Electroactive polymers

ABSTRACT

Electroactive polymeric arylenes and intermediates useful for making such polymers are disclosed. The present invention also provides electroactive compositions comprising the electroactive polymeric arylenes, organic electronic devices which comprise these polymers and compositions, and methods of fabricating these devices.

TECHNICAL FIELD

[0001] This invention relates to electroactive polymers, compositionsand organic electronic devices comprising the electroactive polymers.

BACKGROUND

[0002] Organic electronic devices such as organic electroluminescent(OEL) devices, including organic light emitting diodes (OLEDs), aredesirable for use in electronic media because of their thin profile, lowweight, capability of obtaining a wide variety of emission colors, andlow driving voltage. OLEDs have potential use in applications such asbacklighting of graphics, pixelated displays, and large emissivegraphics.

[0003] There has been continuing research and development ofelectroluminescent materials, electroactive materials, and chargetransporting materials suitable for such devices and methods for makingthe devices. In some instances, materials have been selected ordeveloped which facilitate one or more of these methods.

[0004] Pattern-wise thermal transfer of materials from donor sheets toreceptor substrates has been proposed as one method for forming OELdevices. Selective thermal transfer of organic light emitters forformation of organic electroluminescent devices has been shown to beparticularly useful.

[0005] There remains a need in the art for electroactive polymers andelectroluminescent polymers that may be used in these devices andmethods.

SUMMARY OF THE INVENTION

[0006] The present invention provides electroactive, charge transportingor electroluminescent arylene polymers. In some embodiments, thesepolymers have improved electron transport and electron injectionproperties. The present invention also provides electroactivecompositions, which comprise at least one of these arylene polymers. Thepresent invention also provides novel intermediates for making suchpolymers. The present invention further provides organic electronicdevices comprising these arylene polymers. The present invention furtherprovides methods and materials for making organic electronic devicesfrom these materials including selective thermal patterning ofelectroactive materials comprising the arylene polymers onto a receptor.Organic electroluminescent devices, which can easily be produced usingthe present arylene polymers, have high luminous efficiency and longservice life.

[0007] In one aspect the present invention comprises an electroactivepolymeric arylene. The electroactive polymeric arylene comprises aconjugated internal region, end capping groups, and optionally a softsegment; wherein the conjugated internal region comprises three or morearylene units, each of said arylene units being covalently bonded to twoadjacent arylene units, to an adjacent arylene unit and to an endcapping group, or to an adjacent arylene unit and to the soft segment ifpresent; wherein one or more of the arylene units of the internal regionhave the structure of Formula I

[0008] wherein Ar¹ is a phenylene or naphthylene group arylene that isunsubstituted or substituted with one or more groups selected fromalkyl, alkenyl, alkoxy, fluoro, aryl, fluoroalkyl, heteroalkyl,heteroaryl, and hydrocarbyl containing one or more S, N, O, P, or Siatoms; where a is 1 or 2; where each E_(y) is independently selectedfrom groups having the structures of Formulas II and III

[0009] wherein X is O, S, or NR¹, where R¹ is alkyl, aryl, heteroaryl,or heteroalkyl; wherein each R² is independently selected from alkyl,alkoxy, fluoro, aryl, fluoroalkyl, heteroalkyl, and heteroaryl; whereinb is 0, 1, or 2; wherein Ar² is a carbocyclic aryl group, unsubstitutedor substituted with one or more substituents selected from alkyl,alkenyl, alkoxy, fluoro, aryl, fluoroalkyl, heteroalkyl, heteroaryl,alkyloxadiazolyl, aryloxadiazolyl, alkyltriazolyl, aryltriazolyl, andhydrocarbyl containing one or more S, N, O, P, or Si atoms; and whereinthe end capping groups are each independently selected from carbocyclicaryl, heteroaryl, and tertiary aromatic amino groups that areelectrochemically stable, wherein each end capping group is conjugatedto the conjugated internal region or bonded to the soft segment ifpresent, and wherein each end capping group is unsubstituted orsubstituted with one or more groups selected from alkyl, alkenyl,alkoxy, aryl, fluoroalkyl, heteroalkyl, heteroaryl, and hydrocarbylcontaining one or more S, N, O, P, or Si atoms.

[0010] In one embodiment the electroactive polymeric arylene describedabove further comprises one or more comonomer units independentlyselected from carbocyclic arylene, heteroarylene, and tertiary aromaticamino arylene groups that modify one or more properties of theelectroactive polymeric arylene selected from light absorption, lightemission, ionization potential, electron transport, hole transport,electroluminescence, and solubility parameter. Preferably the comonomerunits are conjugated with Ar¹ of Formula I. The comonomer units areunsubstituted or substituted with one or more groups selected fromalkyl, alkenyl, alkoxy, fluoro, aryl, fluoroalkyl, heteroalkyl,heteroaryl, and hydrocarbyl containing one or more S, N, O, P, or Siatoms.

[0011] In a second aspect, the present invention also relates to novelintermediates useful for making the electroactive polymeric arylenes.More specifically, this invention relates to monomer units having thestructure of Formula IV:

[0012] where Ar¹, E_(y) and a are as described for Formula I; and whereD is a reactive group selected from chlorine, bromine, iodine, boronicacid, and boronic ester.

[0013] In a third aspect, the present invention also provideselectroactive compositions that comprise one or more of theelectroactive polymeric arylenes.

[0014] In a fourth aspect, the present invention also provides organicelectronic devices that comprise the electroactive polymeric arylenes orthe electroactive compositions of the present invention.

[0015] In a fifth aspect, the present invention also provides a donorsheet comprising a composition, which comprises one or more of thepresent electroactive polymeric arylenes and a method for making anorganic electronic device comprising the step of selectivelytransferring a composition, which comprises one or more of the presentelectroactive polymeric arylenes, from the donor sheet to a receptorsubstrate.

BRIEF DESCRIPTION OF THE DRAWINGS

[0016] The invention may be more completely understood in considerationof the following detailed description of various embodiments of theinvention in connection with the accompanying drawings, in which:

[0017]FIG. 1 is a schematic side view of an organic electroluminescentdisplay construction of the present invention;

[0018]FIG. 2 is a schematic side view of a donor sheet for transferringmaterials of the present invention;

[0019]FIG. 3 is a schematic side view of an organic electroluminescentdisplay of the present invention;

[0020]FIG. 4A is a schematic side view of a first embodiment of anorganic electroluminescent device of the present invention;

[0021]FIG. 4B is a schematic side view of a second embodiment of anorganic electroluminescent device of the present invention;

[0022]FIG. 4C is a schematic side view of a third embodiment of anorganic electroluminescent device of the present invention;

[0023]FIG. 4D is a schematic side view of a fourth embodiment of anorganic electroluminescent device of the present invention;

[0024]FIGS. 5 and 6 are emission spectra of polymers of the presentinvention; and

[0025]FIGS. 7 and 8 are digital images of a thermally transferredorganic electroluminescent lamp device of the present invention.

DETAILED DESCRIPTION OF THE INVENTION

[0026] Definitions

[0027] As used herein, “a” or “an” or “the” are used interchangeablywith “at least one”, to mean “one or more” of the element beingmodified.

[0028] Unless otherwise indicated, the term “alkyl” includes bothstraight-chained, branched, and cyclic alkyl groups and includes bothunsubstituted and substituted alkyl groups. Unless otherwise indicated,the alkyl groups typically contain from 1 to 20 carbon atoms. Examplesof “alkyl” as used herein include, but are not limited to, methyl,ethyl, n-propyl, n-butyl, n-pentyl, isobutyl, t-butyl, isopropyl,n-octyl, n-heptyl, ethylhexyl, and the like.

[0029] Unless otherwise indicated, the term “heteroalkyl” includes bothstraight-chained, branched, and cyclic alkyl groups with one or moreheteroatoms independently selected from S, O, N, P, and Si and includesboth unsubstituted and substituted alkyl groups. Unless otherwiseindicated, the heteroalkyl groups typically contain from 1 to 20 carbonatoms. “Heteroalkyl” is a subset of “hydrocarbyl containing one or moreS, N, O, P, or Si atoms” described below. Examples of “heteroalkyl” asused herein include, but are not limited to methoxy, ethoxy, propoxy,3,6-dioxaheptyl, 3-(trimethylsilyl)-propyl, 4-dimethylaminobutanyl, andthe like.

[0030] Unless otherwise indicated, the term “alkenyl” includes bothstraight-chained, branched, and cyclic alkene groups having one or morealiphatic carbon-carbon double bonds and includes both unsubstituted andsubstituted alkenyl groups. Unless otherwise indicated, the alkenylgroups typically contain from 1 to 20 carbon atoms. Examples of“alkenyl” as used herein include, but are not limited to, n-oct-3-enyl,n-hept-6-enyl, and the like.

[0031] In the present invention, the term “aryl” includes carbocyclicaryl, heteroaryl, and tertiary aromatic amino aryl.

[0032] Unless otherwise indicated, the term “carbocyclic aryl” refers tomonovalent aromatic carbocyclic radicals having one to fifteen aromaticrings, such as phenyl, biphenyl, phenylene group aryl as defined infra,or multiple fused rings, such as naphthyl or anthryl, or combinationsthereof. Examples of suitable carbocyclic aryl as used herein includephenyl, biphenyl, naphthyl, acenaphthyl, phenanthryl, anthracenyl,fluorenyl, 9-silafluorenyl, dihydrophenanthryl, perylenyl,spirobisfluorenyl, fluoranthenyl, pyrenyl, dihydropyrenyl,tetrahydropyrenyl, rubrenyl, chrysenyl, benzo[g,h,i]perylenyl, and thelike. When the carbocyclic aryl contains phenylene rings fused withdivalent alkylene, dialkylsilylene, or diarylsilylene radicals, theseradicals are substituted with two or more R³ groups wherein each R³ isindependently selected from hydrogen, C₁₋₃₀ alkyl, C₁₋₃₀ alkenyl, C₆₋₂₀aryl, C₃₋₂₀ heteroaryl, and C₁₋₃₀ hydrocarbyl containing one or more S,N, O, P, or Si atoms.

[0033] In the present invention, the “arylene”, “arylene monomer”, and“arylene unit” include carbocyclic arylene, heteroarylene, and tertiaryaromatic amino arylene.

[0034] Unless otherwise indicated, the term “carbocyclic arylene” refersto divalent aromatic carbocyclic radicals having one to fifteen aromaticrings, such as phenylene, phenylene group arylene as defined infra, ormultiple fused rings, such as naphthylene or anthrylene, or combinationsthereof. Examples of suitable “carbocyclic arylene” as used hereininclude benzene-1,3-diyl, benzene-1,4-diyl, naphthalene-2,7-diyl,naphthalene-2,6-diyl, naphthalene-1,4-diyl, naphthalene-1,5-diyl,acenaphthenediyl, phenanthen-3,8-diyl, 5,6-dihydrophenathren-3,8-diyl,4,5,9,10-tetrahydropyren-2,7-diyl, pyren-2,7-diyl, fluoren-2,7-diyl,9-silafluoren-2,7-diyl, anthracene-9,10-diyl, perylene-3,9-diyl,perylene-3,10-diyl, spirobisfluorenediyl, fluoranthenediyl, rubrenediyl,chrysenediyl, benzo[g,h,i]perylenediyl and the like. When thecarbocyclic arylene contains phenylene rings fused with divalentalkylene, dialkylsilylene, or diarylsilylene radicals, these radicalsare substituted with two or more R³ groups wherein each R³ isindependently selected from hydrogen, C₁₋₃₀ alkyl, C₁₋₃₀ alkenyl, C₆₋₂₀aryl, C₃₋₂₀ heteroaryl, and C₁₋₃₀ hydrocarbyl containing one or more S,N, O, P, or Si atoms.

[0035] Unless otherwise indicated, the term “phenylene group arylene”refers to divalent aromatic carbocyclic radicals having one, two, orthree conjugated phenylene rings (e.g. phenylene, biphenylene, andtriphenylene) that are optionally fused with divalent alkylene,dialkylsilylene, or diarylsilylene radicals. Examples of suitable“phenylene group arylene” as used herein include benzene-1,3-diyl,benzene-1,4-diyl, 5,6-dihydrophenathren-3,8-diyl,4,5,9,10-tetrahydropyren-2,7-diyl, fluoren-2,7-diyl,9-silafluoren-2,7-diyl, spirobisfluoren-2,7-diyl, 6,12-dihydroindeno[1,2-b]fluorene-2,8-diyl,5,6,12,13-tetrahydrodibenzo[a,h]anthracene-3,10-diyl,5,12-dihydro-6H-indeno[1,2-b]phenathrene-3,10-diyl, and the like.

[0036] Unless otherwise indicated, the term “phenylene group aryl”refers to monovalent unsaturated aromatic carbocyclic radicals havingone, two, or three conjugated phenyl or phenylene rings (e.g. phenyl,biphenyl, and terphenyl) that are optionally fused with divalentalkylene, dialkylsilylene, or diarylsilylene radicals. Examples ofsuitable “phenylene group aryl” as used herein include phenyl,5,6-dihydrophenathrenyl, 4,5,9,10-tetrahydropyrenyl, fluorenyl,9-silafluorenyl, spirobisfluorenyl, 6,12-dihydroindeno[1,2-b]fluorenyl,5,6,12,13-tetrahydrodibenzo[a,h]anthracenyl,5,12-dihydro-6H-indeno[1,2-b]phenathrenyl, and the like.

[0037] Unless otherwise indicated, the term “naphthalene group arylene”refers to divalent unsaturated aromatic carbocyclic radicals having afused naphthalene ring structure, which can be fused with a divalentalkylene radical. Examples of suitable “naphthalene group arylene” asused herein include naphthalene-2,7-diyl, naphthalene-2,6-diyl,naphthalene-1,4-diyl, naphthalene-1,5-diyl, and acenaphthene-diyl.

[0038] Unless otherwise indicated, the term “naphthalene group aryl”refers to monovalent unsaturated aromatic carbocyclic radicals having afused naphthalene ring structure, which can be fused with a divalentalkylene radical. Examples of suitable “naphthalene group aryl” as usedherein include naphthalen-2-yl, naphthalen-1-yl, naphthalen-7-yl,naphthalen-6-yl, naphthalen-4-yl, naphthalen-5-yl, and acenaphthenyl.

[0039] Unless otherwise indicated, the term “heteroaryl” refers to anaromatic monovalent radical comprising a monovalent five—toseven—membered aromatic ring radical with one or more heteroatomsindependently selected from S, O, N, and Si. Such a heteroaryl ring maybe optionally fused to one or more heterocyclic ring(s), carbocyclicaryl ring(s), cycloalkenyl ring(s), cycloalkyl ring(s), or to one ormore of another heteroaryl ring(s). Examples of “heteroaryl” used hereininclude, but are not limited to, furyl, thiophenyl, pyrrolyl,imidazolyl, pyrazolyl, triazolyl, tetrazolyl, thiazolyl, oxazolyl,isoxazolyl, oxadiazolyl, thiadiazolyl, isothiazolyl, pyridinyl,pyridazinyl, pyrazinyl, pyrimidinyl, quinolinyl, isoquinolinyl,benzofuryl, benzothiophenyl, indolyl, carbazoyl, benzoxazolyl,benzothiazolyl, benzimidazolyl, cinnolinyl, quinazolinyl, quinoxalinyl,phthalazinyl, benzothiadiazolyl, benzotriazinyl, phenazinyl,phenanthridinyl, acridinyl, and indazolyl, siloles, and the like.

[0040] Unless otherwise indicated, the term “heteroarylene” refers to anaromatic divalent radical comprising a five—to seven—membered aromaticring radical with one or more heteroatoms independently selected from S,O, N, and Si. Such a heteroarylene ring may be optionally fused to oneor more heterocyclic ring(s), heteroaryl ring(s), carbocyclic arylring(s), cycloalkenyl ring(s), or cycloalkyl ring(s). Examples of“heteroarylene” used herein include furan-2,5-diyl, thiophene-2,4-diyl,1,3,4-oxadiazole-2,5-diyl, 1,3,4-thiadiazole-2,5-diyl,1,3-thiazole-2,4-diyl, benzo[1,2,5]thiadiazole-4,7-diyl,1,3-thiazole-2,5-diyl, pyridine-2,4-diyl, pyridine-2,3-diyl,pyridine-2,5-diyl, pyrimidine-2,4-diyl, quinoline-2,3-diyl,1,1-dialkyl-1H-silole-2,5-diyl, and the like.

[0041] Unless otherwise indicated, the term “condensed polycyclicarylene” refers to a subset of the “carbocyclic arylenes” as definedabove that comprise three to fifteen fused aromatic rings. For example,“condensed polycyclic arylene” used herein include acenaphthylene,phenanthrene, anthracene, fluoranthene, pyrene, perylene, benzoperylene,rubrene, chrysene, and corene.

[0042] Unless otherwise indicated, the term “heteroarylenes comprisingimine linkages” refers to a subset of the “heteroarylenes” as definedabove that comprise an imine linkage. Examples of suitable“heteroarylenes comprising imine linkages” include oxadiazoles,N-substituted-triazoles, N-substituted imidazoles, N-substitutedpyrazole oxazoles, isooxazoles, thiazoles, isothiazoles, pyridines,pyridazines, pyrimidines, pyrazines, triazines, tetrazenes,benzoxazoles, benzothiazoles, benzothiadiazoles, quinolines,isoquinolines, cinnolines, quinazolines, quinoxalines, phthalazines,benzotriazines, phenazines, phenanthridines, acridines.

[0043] Unless otherwise indicated, the term “heteroaryls comprisingimine linkages” refers to a subset of the “heteroaryls” as defined abovethat comprise an imine linkage. Examples of suitable “heteroarylscomprising imine linkages” include oxadiazolyls,N-substituted-triazolyls, N-substituted imidazolyls, N-substitutedpyrazolyls, oxazolyls, isooxazolyls, thiazolyls, isothiazolyls,pyridinyls, pyridazinyls, pyrimidinyls, pyrazinyls, triazinyls,tetrazenyls, benzoxazolyls, benzothiazolyls, benzothiadiazolyls,quinolinyls, isoquinolinyls, cinnolinyls, quinazolinyls, quinoxalinyls,phthalazinyls, benzotriazinyls, phenazinyls, phenanthridinyls, andacridinyls.

[0044] Unless otherwise indicated, the term “heteroarylenes that areelectron rich” refers to a subset of the “heteroarylenes” that areelectron rich. Heteroarylenes that are electron rich can donate electrondensity from the heteroatom of the heteroarylene into aπ system that isconjugated to a neighboring π system. Heteroarylenes that are electronrich exhibit electron donating ability that exceeds the electrondonating ability of heteroarylenes comprising imine linkages. Forexample, “heteroarylenes that are electron rich” includediarylsilanoles, thiophenes, bithiophenes, furans, N-alkyl and N-arylcarbazoles, and N-alkyl pyrroles.

[0045] Unless otherwise indicated, the term “heteroaryls that areelectron rich” refers to a subset of the “heteroaryls” that are electronrich. Heteroaryls that are electron rich exhibit electron donatingability that exceeds the electron donating ability of heteroarylscomprising imine linkages. For example, “heteroaryls that are electronrich” include diarylsilanolyls, thiophenyls, bithiophenyls, andfuranyls.

[0046] Unless otherwise indicated, the term “tertiary aromatic amine”refers to a class of molecular compounds comprising one or more tertiarynitrogen centers, each bonded to three aromatic carbon centers. Examplesof suitable “tertiary aromatic amines” used herein includediarylanilines, alkylcarbazole, arylcarbazole, tetraarylediamines suchas N,N,N′N′-tetraarylbenzidines,N,N,N′,N′-tetraaryl-1,4-phenylenediamines,N,N,N′N′-tetraryl-2,7-diaminofluorene derivatives such as those taughtin EP 0 953 624 Al and EP 0 879 868 A2 (both Canon Kabushiki Kaisha),N,N′-bis(3-methylphenyl)-N,N′-bis(phenyl)benzidine (also known as TPD),N,N′-bis(3-naphthalen-2-yl)-N,N′-bis(phenyl)benzidine (also known asNPB), 1,4-bis(carbazolyl)biphenyl (also known as CBP), othertetraaryldiamine derivatives such as those described in Koene et al.,Chem. Mater. 10, 2235-2250 (1998), and in U.S. Pat. Nos. 5,792,557 and5,550,290, and EP 0891121; peraryltriamine derivatives such as thosedescribed in U.S. Pat. No. 6,074,734 and EP 0827367, starburst aminederivatives such as 4,4′,4′-tris(N,N-diarylamino)triphenylamines and1,3,5-tris(4-(N,N-diarylamino)phenyl)benzenes,4,4′,4″-tris(N,N-diphenylamino)triphenylamine (also known as TDATA),1,3,5-tris(4-(N,N-diphenylamino)phenyl)benzenes (TDAPBs), and otherdendridic and spiro amine derivatives as taught in EP 0650955; Tokito etal., Polym. Prep. (Am. Chem. Soc. Div. Polym. Chem.) 38(1), 388-389,(1997); Tanake et al., Chem. Commun. 2175-2176 (1996); and Tokito etal., Appl. Phys. Lett. 70(15), 1929-1931 (1997).

[0047] Unless otherwise indicated, the term “tertiary aromatic aminoaryl” refers to a monovalent aromatic ring radical of a tertiaryaromatic amine as defined above.

[0048] Unless otherwise indicated, the term “tertiary aromatic aminoarylene” refers to a divalent unsaturated aromatic carbocyclic radicalof a tertiary aromatic amine as defined above.

[0049] Unless otherwise indicated, the term “hydrocarbyl” refers tomonovalent radicals containing aliphatic or aromatic groups, orcombinations thereof. Unless otherwise indicated, the hydrocarbyl groupstypically contain from 1 to 60 carbon atoms. Hydrocarbyls containing oneor more S, N, O, P, or Si atoms are also called out. Some examples ofsuch hydrocarbyls as used herein include, but are not limited tomethoxy, ethoxy, propoxy, 4-diphenylaminobutanyl,2-(2′-phenoxyethoxy)ethyl, 3,6-dioxaheptyl, 3,6-dioxahexyl-6-phenyl,9-sila-9,9-(3,6-dioxaheptyl )fluoren-2-yl, and —[Ar]p-SS—R″ where Ar iscarbocyclic arylene or heteroarylene, p is 0 or 1, R″ is a stericallyhindering functional group such as an aryl, heteroaryl, or a branchedalkyl, and SS is a soft segment moiety defined below.

[0050] Unless otherwise indicated, the terms “soft segment”, SS, or“soft segment moiety” refers to a divalent aliphatic group whichincludes two or more groups each independently selected from ethers,fluoroalkylene, perfluoroalkylene, teriary amines, thioethers,dialkylsiloxanes, and dialkoxysiloxanes. Examples of suitable softsegment moieties include, for example, poly(oxyalkylene) groups (e.g.,—O(C_(q)H_(2q)O)_(s)— where q is an integer in the range of 1 to 6 and sis an integer in the range of 2 to 20) and poly(dialkylsiloxanes) (e.g.,[—Si(C_(r)H_(2r+1))₂O—-]_(n), where r is an integer in the range of 1 to10 and n is an integer in the range of 2 to 20). Preferably, SS is apoly(oxyalkylene) containing from 2 to 20 carbon atoms.

[0051] Unless otherwise indicated, each of the above alkyl, alkenyl,carbocyclic aryl, carbocyclic arylene, heteroalkyl, heteroaryl,heteroarylene, polycyclic arylene, and hydrocarbyl groups isunsubstituted or substituted with one or more groups, each independentlyselected from C₁₋₃₀ alkyl, C₁₋₃₀ alkenyl, C₁₋₃₀ alkoxy, C₆₋₂₀ aryl,C₁₋₃₀ heteroalkyl, C₁₋₆₀ hydrocarbyl containing one or more S, N, O. P,or Si atoms, C₃₋₂₀ heteroaryl, C₆₋₂₀ aryloxy, C₁₋₃₀ thioalkyl, C₆₋₂₀thioaryl, diarylamino, fluoro, cyano, —COO—alkyl, fluoroalkyl, andperfluoroalkyl.

[0052] Unless otherwise indicated, the term “copolymer” refers topolymers having two or more different divalent monomer units.

[0053] By “electrochemically stable” is meant stable to electrochemicaldegradation such that any oxidation and/or reduction reactions enteredinto are reversible.

[0054] An asterisk (*) in any of the structures infra indicates the bondto an adjacent group or unit of the compound or polymer in which thestructure resides.

[0055] Polymers

[0056] The electroactive polymeric arylenes described herein can beuseful in organic electronic devices, and in particular OLEDs. In someembodiments, the electroactive polymeric arylenes have improved electrontransport and electron injection properties compared with polymericarylenes that do not contain arylene units of the Formula I. OLEDscomprising these electroactive polymeric arylenes can have increasedlight emission quantum efficiencies and/or reduced operating voltagescompared with OLEDs without the electroactive polymeric arylenes. Theincreased efficiencies can also be maintained over time and repeateduse. Such electroactive polymeric arylenes comprise a conjugatedinternal region, end capping groups, and optionally a soft segment. Eacharylene unit of the internal region is covalently bonded to two adjacentarylene units, to an adjacent arylene unit and to an end capping group,or to an adjacent arylene unit and to the soft segment if present.Vinylene and acetylene units are generally not included in theconjugated internal region of the polymeric arylene because of the lowband-gap and low external quantum efficiencies found withpoly(phenylenevinylenes) (PPV) (see Chung et al., Advanced Materials,10, 1112 (1998) and Meng et al., Macromolecules, 32, 8841 (1999)).

[0057] At least two of the arylene units of the conjugated internalregion have the structure of Formula I:

[0058] where Ar¹ is a carbocyclic arylene group, preferably a phenylenegroup arylene or a naphthalene group arylene, unsubstituted orsubstituted on one or more of the aromatic rings with one or more groups(R^(y)) selected from alkyl, alkenyl, alkoxy, fluoro, aryl, fluoroalkyl,heteroalkyl, heteroaryl, hydrocarbyl containing one or more S, N, O, P,or Si atoms; where a is 1 or 2; where each E_(y) is independentlyselected from groups having the structures of Formulas II and III

[0059] wherein X is O, S, or NR¹, where R¹ is alkyl, aryl, heteroaryl,or heteroalkyl; wherein each R² is independently alkyl, alkenyl, alkoxy,fluoro, aryl, fluoroalkyl, heteroalkyl, or heteroaryl; wherein b is 0,1, or 2; wherein Ar² is a carbocyclic aryl group, unsubstituted orsubstituted on one or more of the aromatic rings with one or more groups(R^(z)) selected from alkyl, alkenyl, alkoxy, fluoro, aryl, fluoroalkyl,heteroalkyl, heteroaryl, alkyloxadiazolyl, aryloxadiazolyl,alkyltriazolyl, aryltriazolyl, diarylaminoaryl, diarylamino, andhydrocarbyl containing one or more S, N, O, P, or Si atoms.

[0060] The end capping groups (EC) are each independently selected fromcarbocyclic aryl, heteroaryl, and tertiary aromatic amino groups thatare electrochemically stable and unsubstituted or substituted with oneor more groups selected from alkyl, alkoxy, alkenyl, aryl, fluoroalky,heteroalkyl, heteroaryl, and hydrocarbyl containing one or more S, N, O,P, or Si atoms, each end capping group being conjugated to theconjugated internal region or bonded to the soft segment if present.

[0061] In some embodiments the electroactive polymeric arylenes of thepresent invention have been found to remain amorphous at temperaturesabove their glass transition temperature. In some embodiments it as alsobeen found that the color of light emission from light emittingelectroactive polymeric arylenes of the present invention remains stableduring thermal aging. That is, the color of the emitted light does notappreciably change during thermal aging. In some embodiments theemission color that does not shift is blue.

[0062] Substituents that are known to be photoluminescent quenchers,such as arylcarbonyls and nitro, may be undesireable as they degradeelectroluminescence efficiency in OLEDs. Substituents that are known toundergo electrochemical elimination reactions, such as alkylamines, maybe undesireable because they degrade the operating lifetime of OLEDs.Substituents comprising titratable protons that can undergoelectrochemical reduction, such as primary or secondary amines, phenols,alcohols and the like, may be undesireable since they can be reduced tohydrogen during OLED operation, and lead to delamination of the cathodeand ultimate failure of the OLED. Chlorine, bromine, iodine, boronicacid, and boronic ester substitutents can cause electrochemicalinstability and are typically present in the electroactive polymericarylenes of the present invention in an amount less than 1000 part permillion (ppm) by weight of the polymer, for example, less than 100 ppm.Parafluorophenyl may not be desirable as a capping group because it issusceptible to irreversible electrochemical degradation.

[0063] The end capping group (EC) can serve many functions relevant toOLED device performance and to the fabrication of these devices. Thestable carbocyclic aryl capping groups mentioned above include phenylenegroup and naphthalene group aryls and condensed polycyclic aryls. Thephenylene group and naphthalene group aryls can provide anelectrochemically stable end group, while also providing an electronaffinity for the highest occupied molecular orbital (HOMO) and anionization potential for the lowest unoccupied molecular orbital (LUMO)that are well matched to the conjugated polymer backbone structurescomprising Ar¹ groups. By well matched it is meant that the HOMO andLUMO of EC are close in energy (for example, 0.5 eV or 0.25 eV) to theHOMO and LUMO, respectively, of the conjugated internal region of thepolymer. This energy match and a large bandgap between the HOMO and LUMOare particularly important when a high bandgap polymer is desired foruse as an electron transport agent, a hole blocker, as a host polymerfor molecular blue emitters, or as a blue emitting electroluminescentpolymer. In these cases, low energy traps must be avoided as they candegrade device performance.

[0064] Stable condensed polycyclic aryl, heteroaryl or tertiary aromaticamino aryl end capping groups mentioned above can provide anelectrochemically stable end group, while also introducing redox activefunctional groups that can further enhance electron transport character,introduce hole transport character, enhance or modify the band gapand/or electroluminescent character of the polymer. Certain of these endcapping groups, when incorporated at terminal positions in a polymericarylene of the present invention, will give rise to specific emissions,for example, red, green, or blue. This is particularly useful whentuning the emission wavelength of an electroluminescent oligomer orpolymer comprising arylene units of Formula I. The stable condensedpolycyclic aryl end capping groups can modify energetics to stabilizeterminal positions with respect to excimer formation and emissionwavelength. The stable heteroaryl or tertiary aromatic amino arylcapping groups are also important when balancing the hole and electrontransport efficiencies, or tuning the ionization potential and/orelectron affinity of the end capping group to other conjugated units ofan electroactive and /or electroluminescent polymer comprising aryleneunits of Formula I, for example to improve the electroluminescentquantum efficiency for the polymer, or to energetically match thepolymer to a molecular emitter in molecularly doped polymer filmconstructions for OLEDs. In addition, these groups may be sufficientlysterically hindering to reduce the formation of intermolecular orintramolecular configurations (of the light emitting polymers) thatproduce excimer or exciplex emission that can cause color shifting ofthe electroluminescence.

[0065] Examples of carbocyclic arylene groups and substitution patternsuseful for —Ar¹(E_(y))_(a)— are represented by Formulas XI-XLIII below,each of which is a subgenus of Formula I, wherein each E_(y) isindependently selected from the pendant groups of Formulas II and IIIabove, wherein Ar¹ is unsubsituted or substituted on one or more of thearomatic rings with one or more groups (R^(y)); wherein each R³ isindependently selected from hydrogen, C₁₋₃₀ alkyl, C₁₋₃₀ alkenyl, C₆₋₂₀aryl, C₃₋₂₀ heteroaryl, and C₁₋₃₀ hydrocarbyl containing one or more S,N, O, P, or Si atoms; and wherein R^(y) is independently selected fromfluoro, C₁₋₂₀ fluoroalkyl, C₁₋₂₀ perfluoroalkyl, C₁₋₂₀ alkyl, C₁₋₂₀alkenyl, C₆₋₂₀ aryl, C₃₋₂₀ heteroaryl, and C₁₋₃₀ hydrocarbyl containingone or more S, N, O, P, or Si atoms.

[0066] Some examples of carbocyclic aryl groups and substitutionpatterns useful for Ar² are represented by Formulas XLIV-LIV below whereAr² is unsubstituted or substituted on one or more of the aromatic ringswith one or more groups (R^(z)); where R³ is independently in each casehydrogen, C₁₋₃₀ alkyl, C₁₋₃₀ alkenyl, C₆₋₂₀ aryl, C₃₋₂₀ heteroaryl, orC₁₋₃₀ hydrocarbyl containing one or more S, N, O, P, or Si atoms; whereR^(z) is independently in each case fluoro, C₁₋₂₀ fluoroalkyl, C₁₋₂₀perfluoroalkyl, C₁₋₂₀ alkyl, C₁₋₂₀ alkenyl, C₆₋₂₀ aryl, C₃₋₂₀heteroaryl, C₁₋₃₀ hydrocarbyl containing one or more S, N, O, P, or Siatoms; C₃₋₃₀ alkyloxadiazolyl, C₃₋₃₀ aryloxadiazolyl, C₃₋₃₀alkyltriazolyl, C₃₋₃₀ aryltriazolyl; and where X is O, S, or NR, whereinR¹ is alkyl, aryl, heteroaryl, or heteroalkyl.

[0067] In some embodiments electroactive polymeric arylenes of thepresent invention exhibit improved electron transport properties and,where desired, large exciton energy to prevent energy transfer of theexcitons. Furthermore, through incorporation of substituent groups R¹,R², R³, R^(y), and R^(z) described supra, we have found that we canimprove the solubility of polymeric arylenes in organic solvents andthat the films made from these polymeric arylenes remain amorphous asthin films, by suppressing aggregation and phase separation. Furthermorethese materials are typically free of polymerization by-products thatdegrade OLED performance, such as terminal aryl halides.

[0068] In some embodiments the electroactive arylene polymers of thepresent invention serve as effective n-type electron transport hostmaterials for making solution processible molecularly doped polymercompositions that can serve as the emissive organic element in OLEDdevices. In addition, difunctional electroactive carbocyclic arylenemonomers of the present invention can be copolymerized into lightemitting polymers to enhance electron transport character withoutadversely affecting the emission characteristics of the polymers.

[0069] One exemplary embodiment of the electroactive polymeric arylenesof this invention are endcapped polymers as illustrated in Formula V:

[0070] where a=1 or 2; n is an integer in the range of 3 to 100,000, 10to 10,000, or 20 to 2,000; Ar¹ and E_(y) are as described above forFormulas I-III; and EC is an end capping group as described supra. Thesepolymers may optionally comprise a soft segment moiety in the polymerbackbone or pendent from any of the arylene units or end capping groupsto improve processibility. When E_(y) and a are not the same on all Ar¹units, the polymer can be a random, alternating, or block copolymer.

[0071] These polymers can be used effectively as electron transportlayers or as a component therein with good hole blocking characteristicin a multilayer OLED device. These polymers can also be used as anactive electron transport host when blended with hole transport agentsand emissive dopants to create high efficiency electroluminescent layersfor OEL devices. This may be done, for example, by blending the polymerwith a hole transport material and an emissive dopant, spin coating orotherwise applying the mixture onto a suitable transparent anodesubstrate and depositing a cathode.

[0072] For certain choices of Ar¹ (e.g. certain 2,7-fluorenylenes,paraphenylenes) the polymers of Formula V exhibit strongelectroluminescence in the absence of an emissive dopant. These polymersexhibit improved electron transport character compared to correspondingpolymers not comprising the pendant E_(y) groups. The pendant E_(y)groups can also confer improved processibility (e.g., solubility,thermal transferability, web processiblity, solution coatability) forthese polymers relative to corresponding polymers without the E_(y)groups.

[0073] Examples of useful electroactive polymeric arylene polymers ofFormula V include, but are not limited to homopolymers of FormulasLV-LXVII

[0074] Some examples of useful end capping groups (EC) include, but arenot limited to the groups of Formulas LXVIII-LXXXVIII:

[0075] In Formulas LXVIII-LXXXVII, R³ is independently in each casehydrogen, C₁₋₃₀ alkyl, C₁₋₃₀ alkenyl, C₆₋₂₀ aryl, C₃₋₂₀ heteroaryl, orC₁₋₃₀ hydrocarbyl containing one or more S, N O, P, or Si atoms, forexample, octyl, and wherein any of the aromatic or aliphatic rings canbe independently substituted one or more times with fluoro, C₁₋₂₀fluoroalkyl, C₁₋₂₀ perfluoroalkyl, C₁₋₂₀ alkyl, C₁₋₂₀ alkenyl, C₆₋₂₀aryl, C₃₋₂₀ heteroaryl, or C₁₋₃₀ hydrocarbyl containing one or more S,N, O, P, or Si atoms, for example, octyloxy.

[0076] Any of the end capping groups, EC, shown above in FormulasLXVIII-LXXXVIII, prepared in the Examples, or otherwise described hereincan be used to cap any of the polymers described herein. For example,the 7-bromo or 7-(4,4,5,5-tetramethyl-1,3,2-dixaborolan-2-yl) of the ECof Formula LXXVIII can be used in place of bromobenzene in Example 25 toform the corresponding copolymer capped with the EC of Formula LXXVIII.

[0077] In another exemplary embodiment of the present invention, theelectroactive polymeric arylenes described supra are copolymers. Theseelectroactive polymeric arylenes are terminally capped copolymerswherein one or more of the arylene units are comonomer units, eachindependently selected from a different arylene unit of Formula I,carbocyclic arylene, heteroarylene, and/or tertiary aromatic aminoarylene, wherein the comonomer units are conjugated with Ar¹. Thecomonomer units are unsubstituted or substitued with one or more groupsindependently selected from alkyl, alkenyl, fluoro, aryl, fluoroalkyl,heteroalkyl, heteroaryl, and hydrocarbyl containing one or more S, N, O,P, or Si atoms. These copolymers may optionally comprise a soft segmentmoiety, further described infra, in the polymer backbone or pendent froman arylene unit or end capping group to improve processibility (e.g.,solubility, thermal transferability, web processiblity, solutioncoatability) for these polymers relative to corresponding polymerswithout a soft segment moiety. The incorporation of the additionalcarbocyclic arylene, heteroarylene, and/or tertiary aromatic aminoarylene units into the polymeric arylene may be used to modify the lightabsorption, light emission, ionization potential, electron affinity,solubility parameter, and/or electron and hole conducting properties ofthe polymeric arylene.

[0078] Many electronic applications require the active material toexhibit both hole transporting and electron transporting propertieswithout the addition of molecular transport agents. To maximize theefficiency of an OLED, for example, the polymer should ideally transportboth holes and electrons equally well (Bradley et al., inSpringer-Verlag Berlin Heidelberg, 1992, pp. 304-309). However, inpractice this is difficult to achieve. Condensed polycyclic arylenes andheteroarylenes comprising imine linkages can be polymerized directlyinto the polymer backbone to increasing the electron transport characterof the polymer. However, these groups simultaneously shift the emissionwavelength due to resonance effects (Zhan et al., Macromol. 35,2529-2537 (2002), Tsvie et al., J. Mater. Chem. 9,2189-2200 (1999), U.S.Pat. No. 4,597,896). This makes it difficult to use these types ofmonomers to simultaneously balance electron transport character and tunethe emission of the polymer. Furthermore, polymers with conjugatedoxadiazoles have been shown to provide only mediocre electron transportproperties (Li et al., Mat. Res. Soc. Symp. Proc. 413, 13-22 (1996)).

[0079] Applicants have now discovered that electron transport propertiescan be introduced into arylene based polymers using the electroactivearylene units of Formula I. Surprisingly, these units can be introducedin relatively high amounts into a wide range of arylene based polymerswithout affecting the emission characteristics of the polymer.

[0080] Suitable copolymers of the invention are illustrated, forexample, by Formulas VI, VII, and VIII

[0081] wherein electroactive arylene units —Ar¹(E_(y))_(a)- are asdefined for Formula I supra and may be the same or different; whereinAr³ and Ar⁴ are each independently selected from C₆₋₂₀ carbocyclicarylenes, C₃₋₂₀ heteroarylenes, and C₁₈₋₆₀ tertiary aromatic aminoarylenes and are unsubstituted or substituted with one or moresubstituents (R^(x)) selected from alkyl, aryl, heteroaryl, andhydrocarbyl containing one or more S, N, O, P, or Si atoms; wherein mand n are integers in the range of 2 to 100,000; and wherein the endcapping groups (EC) are the same or different and are electrochemicallystable aryl, heteroaryl, or tertiary aromatic amino aryl groups orcombinations thereof as described supra. These copolymers may optionallycomprise a soft segment moiety in the polymer backbone or pendent to anarylene unit or end capping group to improve processibility (e.g.,solubility, thermal transferability, web processiblity, solutioncoatability) for these polymers relative to corresponding polymerswithout a soft segment moiety. The soft segment moiety is divalent ormonovalent; the divalent soft segments being bonded to two of the groupsor units selected from EC and Ar¹, EC and Ar³, EC and Ar⁴, Ar¹ and Ar¹,Ar³ and Ar³, Ar¹ and Ar³, Ar¹ and Ar⁴, and Ar³ and Ar⁴; and themonovalent soft segments being pendent to one or more of EC, Ar¹, Ar³,Ar⁴, or E_(y). These polymers may be random, alternating, or blockcopolymers. Alternating and block coplymers are particularly suitable.

[0082] Suitable carbocyclic arylene, heteroarylene, and tertiaryaromatic amino arylene units for Ar³ and Ar⁴ in Formulas VI-VIII can beselected based on the desired function for the polymer (e.g. electrontransport-hole blocking polymer, electroluminescent polymer, hostpolymer for molecularly doped polymer films) and on the functionalattributes of the comonomer units. In this context, the comonomer unitscan be subdivided into one of three categories based on their function:high band gap units, hole transport units, and electron transport units.High bandgap means that the energy difference between the HOMO and LUMOof the monomoer or copolymer unit or polymer comprising the monomer orcopolymer unit is at least 2.5 eV, for example 3 eV. Light emittingpolymers with a high bandgap function can provide emission of blue orblue-green light and have a bandgap of at least 2.5 eV. Host polymerswith a bandgap of at least 2.5 eV, for example 3 eV, can serve as usefulhost polymers for polymeric, oligomeric, or molecular emitters of bluelight.

[0083] In some embodiments Ar³ and/or Ar⁴ can provide high bandgapfunction when Ar³ and/or Ar⁴ in Formulas VI-VIII are selected fromphenylene group arylene units and naphthalene group arylene units. Insome exemplary embodiments of copolymers of Formulas VI-VIII, one orboth of Ar³ and Ar⁴ are fluorenylene of Formula LXXXIX

[0084] wherein R³ is independently in each case selected from hydrogen,C₁₋₃₀ alkyl, C₁₋₃₀ alkenyl, C₆₋₂₀ aryl, C₃₋₂₀ heteroaryl, and C₁₋₃₀hydrocarbyl containing one or more S, N, O, P, or Si atoms; whereinR^(y) is independently in each case selected from fluoro, C₁₋₂₀fluoroalkyl, C₁₋₂₀ perfluoroalkyl, C₁₋₂₀ alkyl, C₁₋₂₀ alkenyl, C₆₋₂₀aryl, C₃-₂₀ heteroaryl, and C₁₋₃₀ hydrocarbyl containing one or more S,N, O, P, or Si atoms; and wherein n is 0, 1, or 2, in combination with—Ar¹(E_(y))_(a)- selected from Formulas XI-XLIII. In some embodiments—Ar¹(E_(y))_(a)- is selected from Formulas XXXI-XXXIV. In at least someof these embodiments, the copolymers are electroluminescent and,surprisingly, provide stable emission of blue light (or green lightdepending upon the selection of Ar³ or Ar⁴) with improved electrontransport efficiencies. Incorporation of the —Ar¹(E_(y))_(a)- units intoa polyfluorene backbone unexpectedly eliminated excimer formation andcrystallization responsible for color shifting observed with previouslyknown blue light emitting poly(dialkylfluorenes).

[0085] Some electron transport character and significant color tuningcan be introduced if Ar³ and Ar⁴ in Formulas VI-VIII are electrondeficient monomer units selected from arylene units that are condensedpolycyclic arylene units and heteroarylene units comprising iminelinkages as defined above, or both.

[0086] Hole transport character and some color tuning can be introducedif Ar³ and Ar⁴ in Formulas VI-VIII are electron rich monomer unitsselected from heteroarylenes that are electron rich and tertiaryaromatic amino arylenes as defined above, or both.

[0087] Non-limiting examples of divalent hole transport units useful inthe present invention include tertiary aromatic amino arylenes ofFormulas XC-XCVI

[0088] wherein R^(x) is as defined above in Formulas VI-VIII.

[0089] Through selection of Ar¹, Ar³ and Ar⁴, delocalized emissioncenters can be incorporated into the polymer. For example, condensedpolycyclic arylenes and heteroarylenes comprising imine linkages can beincorporated selectively into the conjugated backbone structures ofotherwise phenylene group and naphthalene group conjugated arylenepolymers to provide centers for exciton recombination, giving rise tocharacteristic emissions. As examples, the condensed polycyclic arylenesderived from anthracene, perylene and pyrene can be incorporated withadjacent carbocyclic arylene, heteroarylene, or aromatic amino aryleneunits to give blue or green electroluminescence (Millard, SyntheticMetals, 111-112, 119-123 (2000), Bernius et al., Advanced Mater. 12,1737-1750 (2000)). The same is true for several of the heteroarylenescomprising imine linkages, most notably the benzothiadiazol-4,7-diyl.

[0090] In some embodiments of the electroactive polymeric aryleneterminally capped copolymers of Formulas VI-VIII, Ar³ and Ar⁴ areindependently selected from phenylene group arylenes and naphthalenegroup arylenes wherein each phenylene group arylene and naphthalenegroup arylene is independently unsubstituted or substituted with one ormore substituents (R^(x)) selected independently in each case fromfluoro, C₁₋₂₀ fluoroalkyl, C₁₋₂₀ perfluoroalkyl, C₁₋₂₀ alkyl, C₆₋₂₀aryl, C₃₋₂₀ heteroaryl, and C₁₋₃₀ hydrocarbyl containing one or more S,N, O, P, or Si atoms. In one embodiment, for example, the electroactivepolymeric arylene copolymers comprise at least 5% of the electroactivearylene units of Formula I, and at least 10% of comonomer unitsindependently selected from phenylene group arylenes and naphthalenegroup arylenes. In another embodiment, the copolymers comprise at least15% of the electroactive arylene units of Formula I, and at least 10% ofthe phenylene group or naphthalene group arylene units, unsubstituted orsubstituted as described above. In yet another embodiment, thecopolymers comprise at least 20% of the electroactive arylene units ofFormula I, and at least 20% of the phenylene group or naphthalene grouparylene units, unsubstituted or substituted as described above. Theratios of different electroactive arylene units of Formula I may varywithout limit and the ratio of different phenylene group or naphthalenegroup arylene units may vary without limit. When the ratio varieswithout limit, one unit in the ratio may be absent while the other unitprovides 100% of this type of unit. The above % values for each of thearylene units are based on the total number of repeat units in thecopolymer.

[0091] As with the homopolymers, these copolymers can be usedeffectively as electron transport layers with good hole blockingcharacteristic in a multilayer OLED device. These copolymers can also beused as an active electron transport host when blended with molecularhole transport agents and emissive dopants to create high efficiencyelectroluminescent devices. For certain choices of Ar¹, Ar³, and Ar⁴,polymerization gives rise to extended conjugation in the polymerbackbone (e.g. oxadiazolyl substituted poly(2,7-fluorenes) oroxadiazolyl substituted polyparaphenylenes) that can provideelectoluminescent polymers with improved electron transport charactercompared with the same polymers not comprising the electroactive aryleneunits of Formula I.

[0092] Examples of useful electroactive polymeric arylene copolymerscomprising electroactive arylene units of Formula I and phenylene groupor naphthalene group arylene units include, but are not limited to thoseof the Formulas XCVII-CII

[0093] wherein EC is as described supra.

[0094] In some embodiments of the electroactive polymeric arylenecopolymers of the present invention, the terminally capped copolymers ofFormulas VI-VIII are preferably alternating or block copolymers, whereinAr³ and Ar⁴ are independently selected from condensed polycyclicarylenes, heteroarylenes, and tertiary aromatic amino arylenes, whereinthe condensed polycyclic arylenes, heteroarylenes, and tertiary aromaticamino arylenes are independently unsubstituted or substituted with oneor more substituents (R^(x)) selected independently in each case fromC₁₋₂₀ alkyl, C₆₋₂₀ aryl, C₃₋₂₀ heteroaryl, and C₁₋₃₀ hydrocarbylcontaining one or more S, N, O, P, or Si atoms. In one embodiment thecopolymers comprise at least 10% of the electroactive arylene units—Ar¹(E_(y))_(a)- of Formula I, and at least 1% of comonomer unitsselected from electron rich heteroarylenes and tertiary aromatic aminoarylenes; said electron rich heteroarylene or tertiary aromatic aminoarylene units being unsubstituted or substituted with one or moresubstituents (R^(x)) as above. In another embodiment, the copolymerscomprise at least 15% of the electroactive arylene units of Formula I,and at least 10% of electron rich heteroarylene or tertiary aromaticamino arylene units, unsubstituted or substituted as described above. Inanother embodiment, the copolymers comprise at least 20% of theelectroactive arylene units of Formula I, and at least 20% of electronrich heteroarylene or tertiary aromatic amino arylene units,unsubstituted or substituted as described above. The ratios of differentelectroactive arylene units —Ar¹(E_(y))_(a)- of Formula I may varywithout limit and the ratio of different electron rich heteroarylene ortertiary aromatic amino arylene units may vary without limit. When theratio varies without limit, one unit in the ratio may be absent whilethe other unit provides 100% of this type of unit. The above % valuesfor each of the arylene units are based on the total number of repeatunits in the copolymer. These polymers provide both hole and electrontransport properties and optionally are electroluminescent. They serveas useful host materials for blended electroluminescent compositions.

[0095] In some embodiments of the electroactive polymeric arylenecopolymers of the present invention, the terminally capped copolymers ofFormulas VI-VIII are preferably block copolymers, wherein Ar³ and Ar⁴are independently selected from electron rich heteroarylenes or tertiaryaromatic amino arylenes, phenylene group arylenes and naphthalene grouparylenes, wherein the electron rich heteroarylenes or tertiary aromaticamino arylenes, phenylene group arylenes and naphthalene group arylenesare unsubstituted or substituted with one or more substituents (R^(x))selected independently in each case from fluoro, C₁₋₂₀ fluoroalkyl,C₁₋₂₀ perfluoroalkyl, C₁₋₂₀ alkyl, C₆₋₂₀ aryl, C₃₋₂₀ heteroaryl, andC₁₋₃₀ hydrocarbyl containing one or more S, N, O, P, or Si atoms. In oneembodiment the copolymers comprise at least 5% of the electroactivearylene units —Ar¹(E_(y))_(a)- of Formula I, at least 1% of electronrich heteroarylenes or tertiary aromatic amino arylenes, and at least10% of phenylene group arylenes or naphthalene group arylenes,unsubstituted or substituted as above. In another embodiment, thecopolymers comprise at least 10% of the electroactive arylene units ofFormnula I, at least 10% of the electron rich heteroarylenes or tertiaryaromatic amino arylenes, unsubstituted or substituted as describedabove, and at least 15% of the phenylene group arylenes or naphthalenegroup arylenes, unsubstituted or substituted as described above. Inanother embodiment, the copolymers comprise at least 20% of theelectroactive arylenes of Formula I, at least 20% of electron richheteroarylenes or tertiary aromatic amino arylenes, unsubstituted orsubstituted as described above, and at least 30% of the phenylene grouparylenes or naphthalene group arylenes, unsubstituted or substituted asdescribed above. The ratios of different electroactive arylene units—Ar¹(E_(y))_(a)- of Formula I may vary without limit; the ratio ofdifferent electron rich heteroarylene or tertiary aromatic amino aryleneunits may vary without limit; the ratio of different phenylene grouparylene or naphthalene group units may vary without limit. When theratio varies without limit, one unit in the ratio may be absent whilethe other unit provides 100% of this type of unit. The above % valuesfor each of the arylene units are based on the total number of repeatunits in the copolymer. The conjugated internal region (conjugatedbackbone) of these polymers supports electron delocalization requiredfor electroluminescence, as well as electronically conjugated hole andelectron transport functionality.

[0096] In some embodiments of the electroactive polymeric arylenecopolymers of the present invention, the terminally capped copolymers ofFormulas VI-VIII are preferably alternating copolymers, wherein Ar³ andAr⁴ are independently selected from condensed polycyclic arylene,heteroarylene comprising imine linkage, electron rich heteroarylene,tertiary aromatic amino, phenylene group arylene, and naphthalene grouparylene, each of which is independently unsubstituted or substitutedwith one or more substituents (R^(x)) selected independently in eachcase from fluoro, C₁₋₂₀ fluoroalkyl, C₁₋₂₀ perfluoroalkyl, C₁₋₂₀ alkyl,C₆₋₂₀ aryl, C₃₋₂₀ heteroaryl, and C₁₋₃₀ hydrocarbyl containing one ormore S, N, O, P, or Si atoms. In one embodiment, the these copolymerscomprise at least 5% of the electroactive arylene units —Ar¹(E_(y))_(a)-of Formula I, at least 1% of condensed polycyclic arylene orheteroarylene comprising imine linkage, optionally at least 1% ofelectron rich heteroarylene or tertiary aromatic amino, and optionallyat least 10% of phenylene group arylene or naphthalene group arylene. Inanother embodiment, the copolymers comprise at least 10% of theelectroactive arylene units of Formula I, at least 5% of one or morecondensed polycyclic arylene or heteroarylene comprising imine linkage,at least 10% of electron rich heteroarylene or tertiary aromatic aminoarylene, and at least 15% of the phenylene group arylene or naphthalenegroup arylene. In another embodiment, the copolymers comprise at least20% of the electroactive arylene units of Formula I, at least 10% ofcondensed polycyclic arylene or heteroarylenes comprising imine linkage,at least 20% of electron rich heteroarylene or tertiary aromatic aminoarylene, and at least 30% of the phenylene group arylene or naphthalenegroup arylene. The ratios of different electroactive arylene units—Ar¹(E_(y))_(a)- of Formula I may vary without limit; the ratio ofdifferent electron rich heteroarylene or tertiary aromatic amino aryleneunits may vary without limit; the ratio of different phenylene grouparylene units or naphthalene group arylene units may vary without limit.When the ratio varies without limit, one unit in the ratio may be absentwhile the other unit provides 100% of this type of unit. The above %values for each of the arylene units are based on the total number ofrepeat units in the copolymer. These polymers have a conjugated backboneor conjugated internal region that supports delocalization required forelectroluminescence and color shifting, as well as electronicallyconjugated hole and electron transport functionality.

[0097] Some examples of useful electroactive polymeric arylenecopolymers comprising electroactive arylene units —Ar¹(E_(y))_(a)- ofFormula I and additional comonomers to fine tune the color and chargetransport properties are those of Formulas CIII-CVII

[0098] wherein R^(x) and EC are as defined above in Formulas VI-VIII,and n, m, and l are integers in the range of 2 to 100,000.

[0099] In the copolymers of this invention, electroactive arylene units—Ar¹(E_(y))_(a)- of Formula I, additional comonomers, and capping groupscan be optionally substituted with additional substituents that modifythe solubility parameter, ionization energy, electron affinity, or anycombination of these.

[0100] In one particularly useful embodiment, one or more of Ar^(2,) EC,Ar³, and Ar⁴ are substituted with one or more groups independentlyselected from fluoro, fluoroalkyl, and perfluoroalkyl, with the proviosthat when EC is phenyl, the fluoro group is not in the para position.For example, the substituent groups R³, R^(y), R², and R^(x) associatedwith —Ar¹(E_(y))_(a), the comonomer units, and end capping groups ofpolymers of Formulas V-VIII are independently selected from fluoro,fluoroalkyl, and perfluoroalkyl. Incorporation of these substitutentscan improve the solubility and film forming properties of the polymerand at the same time increase the ionization potential and electronaffinity of the polymer, thereby making it easier to inject electronsand block holes.

[0101] Among other difficulties, some polymers may generate undesirableemission through, for example, excimer formation, as described, forexample, in Neher et al., Macromol. Rapid Commun. 22, 1365-1385 (2001).Substitutents on —Ar¹(E_(y))_(a)-, the comonomer units, and cappinggroups of polymer structures V-VIII can be selected which reduce excimerand exciplex formation, if desired. For example, the substitutents caninclude sterically hindering groups to reduce the formation ofintermolecular or intramolecular configurations of the light emittingpolymers that produce excimer or exciplex emission, which cause colorshifting of the electroluminescence.

[0102] In another useful embodiment, one or more of the substituentgroups R³, R^(y), R^(z), and R^(x) associated with the comonomer and endcapping groups of the polymers of Formulas V-VIII have the generalFormula IX

[0103] where Ar is carbocyclic arylene or heteroarylene, p is 0 or 1, R″is a sterically hindering functional group such as an aryl, heteroaryl,or a branched alkyl, and SS is a soft segment moiety. Preferably, R″ isan aryl. The use of a sterically hindering functional group can reduceor prevent the formation of intermolecular or intramolecular excimerconfigurations. The soft segment moieties are divalent aliphatic groupswhich include two or more functional groups each independently selectedfrom ethers, fluoroalkylenes, perfluoroalkylenes, teriary amines,thioethers, dialkylsiloxanes, and dialkoxysiloxanes. These functionalgroups can be the same or different. Suitable soft segment moietiesinclude, for example, poly(oxyalkylene) groups (e.g.,—O(C_(q)H_(2q)O)_(s)— where q is an integer in the range of 1 to 6 and sis an integer in the range of 2 to 20) and poly(dialkylsiloxanes) (e.g.,[—Si(C_(r)H₂₊₁)₂ 0—]_(n), where r is an integer in the range of 1 to 10and n is an integer in the range of 2 to 20). Preferably, SS is apoly(oxyalkylene) containing from 2 to 20 carbon atoms. In oneembodiment, Ar is phenylene, p is 1, R″ is C₆₋₂₀ carbocyclic aryl (morepreferably, phenyl or biphenyl), and SS is a C₂₋₂₀ poly(oxyalkylene).

[0104] The electroactive polymeric arylenes of the present invention canbe used alone or in combination with each other or with otherelectroactive or light emitting polymers or small molecule materials toform electroluminescent compositions. The soft segments in theelectroactive polymeric arylenes can, if desired, provide bettersolubility parameter matching to a receptor substrate than a similarpolymer without the soft segments. In addition or alternatively, thesoft segments can alter other properties useful to thermal transfer andfilm stability such as, for example, melting temperature, glasstransition temperature, percent crystallinity and tendency tocrystallize or form aggregates, viscosity, thin film morphology,rheological properties such as melt viscosity and relaxation time,excimer and exciplex formation, cohesive strength, and light emissionfrequency, if desired. These soft segment substituents can improvethermal transfer and adhesion of the electroactive polymeric arylenes tocommercially available conducting ionic polymers such as PEDT and PANI,which are commonly used as anode buffer layers in OLED deviceconstructions.

[0105] Soft segments can also be incorporated in the backbone of theelectroactive polymeric arylenes of the present invention, including thepolymeric arylenes of Formulas V-VIII. One illustration of this isrepresented in Formula X

[0106] wherein EC, Ar , —Ar¹(E_(y))_(a)-, and Ar⁴ are as defined inFormulas V-VIII, and SS is a divalent aliphatic group containing two ormore functional groups each independently selected from ethers,fluoroalkylenes, perfluoroalkylenes, teriary amines, thioethers,dialkylsiloxanes, and dialkoxysiloxanes.

[0107] Incorporation of soft segments within the backbone of the polymeror as a pendant group and methods of making the soft segments aredescribed in U.S. Ser. No. 60/374,044 filed on Apr. 19, 2002,incorporated herein by reference.

[0108] A number of methods may be used to make the electroactivepolymeric arylenes of the present invention. For example, the terminallycapped electroactive polymeric arylene homopolymers may be prepared by aprocess wherein a step includes reacting dihalide carbocyclic aryleneintermediates with catalytic anhydrous nickel (II) bromide in thepresence of triphenylphosphine and reducing metal (Zn) according to themethods of Yammamoto et al. (Macromolecules, 25, 1214-1223 (1992)) asmodified by Colon et al. (J. Polym. Sci., Polym. Chem. 28, 367-383(1990)), and applied successfully to fully conjugated polymers by Uedaet al. (Macromolecules, 24, 2694-2697 (1991)), all three referencesfully incorporated herein by reference. In another step the resultinghalide terminated polymer may be capped with an electrochemically inertaryl group by reaction with an excess of a monofunctional aryl group(e.g. 4-bromophenylaniline, 2-bromo-9,9-dioctylfluorene) under standardconditions (i.e., reflux with monofunctional aryl group in toluene forabout 16 hours using tetrakis(triphenylphosphine)palladium (0)catalyst).

[0109] Using the Yammamoto coupling methods, mixtures of monomers eachbearing two halogen substituents (preferably bromine and chlorine) canbe polymerized into copolymers of essentially random nature if themonomers are of about the same reactivity. If reactivities aresignificantly different, then the more reactive monomers would bepolymerized preferentially over the less reactive ones, resulting inblocky copolymers.

[0110] Terminally capped electroactive polymeric arylene homopolymersand alternating copolymers may be prepared by a process wherein a stepincludes reacting arylene dibromide intermediates with arylene diboronicacid/ester intermediates under palladium catalyzed conditions usingSuzuki coupling methods as taught by Miyaura and Suzuki (ChemicalReviews, 95, 2457-2483 (1995)) herein fully incorporated by reference.For example, an arylene dibromide (hereinafter referred to as a type Amonomer) and an arylene diboronic acid/ester (hereinafter referred to asa type B monomer) may be reacted in nearly equal amounts to form desiredalternating copolymers. In another step the resulting halide/boranylterminated polymer may be capped with an electrochemically inert arylgroup by reaction with an excess of a monofunctional aryl group (e.g.bromobenzene/boranylbenzene) under standard Suzuki coupling conditions.

[0111] Terminally capped electroactive arylene copolymers comprisinghole transport, electron transport, and/or emissive monomer units may bemade with the units in a random order using the Yammamoto couplingmethods, or in an alternating order using Suzuki coupling methods. ForSuzuki coupling, two or more type A monomers and two or more type Bmonomers may be reacted so long as the combined molar amount of the typeA monomers is approximately equal to the combined molar amount of thetype B monomers. Alternatively, an excess of type A or type B can beused to control molecular weight. A unique feature of copolymers fromthis process is that chain growth takes place exclusively via theformation of repeating A-B dyads. Such polymers are alternatingcopolymer. Monomers of more complex structure can be employed to yieldcopolymers of even higher degree of structural order. For example, anappropriately functionalized electroactive arylene unit —Ar¹(E_(y))_(a)-of Formula I, may be reacted with two molecules of a carbocyclicarylene, heteroarylene, or tertiary aromatic amine (denoted here asmonomer Ar⁵) to yield a new monomer of the structureBr—Ar⁵—Ar¹(E_(y))_(a)-Ar⁵—Br.

[0112] Block-copolymers comprising block segments of electroactivearylene units —Ar¹(E_(y))_(a)- may also be formed by making reactiveoligomers of these units, along with reactive oligomers of, for examplehole transport monomers, electron transport monomers, soft segmentmonomers, high bandgap monomers(e.g., by Yammamoto or Suzuki couplingmethods), optionally converting the terminal bromides of certain of theoligomers to terminal diboronic acid/ester, or vise versa to provide forboth type A and type B reactive oligomers, and then coupling theresulting reactive oligomers together by Suzuki coupling methods. Endcapping can then be done as described above.

[0113] Reaction Scheme I depicts procedures to access representativeexamples of the block copolymer class of materials by first making tworeactive oligomers. Block copolymers, which comprise a series of onetype of arylene unit bonded to a series of another type of arylene unit,may be made by a polymer extension reaction of, for example, a holetransport oligomer with an electron transport oligomer comprisingelectroactive arylene units —Ar¹(E_(y))_(a)- of Formula I. This can beachieved by the reaction of two or more electroactive oligomers bearingcomplimentary reactive groups (e.g., dibromo and diboronic acid/ester).In step (1a) of Reaction Scheme I the hole transport oligomer isprepared by reaction of the dibromide of a representative tertiaryaromatic amino unit,N,N′-bis(4-bromophenyl)-N,N′-bis(4-butylphenyl)benzene-1,4-diamine, withan excess of the diborolane of a representative electron richheteroarylene,9-phenyl-3,6-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9H-carbazole,under Suzuki coupling conditions to give the borolane-capped holetransport oligomer HT_(B) of Formula CVIII wherein n can vary dependingon the ratio of borolane to bromide used. In one example, the weightaverage molecular weight of the oligomer of Formula CVIII is about 2,400and the oligomer was made as follows. In a 50 mL round bottomed flaskfitted with a rubber septum and reflux condenser were introduced9-phenyl-3,6-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9H-carbazole(0.79 g, 1.59 mmole, 5 equivalents) from Part A of Example 13 infra,N,N′-bis(4-bromophenyl)-N,N′-bis(4-butylphenyl)benzene-1,4-diamine (0.65g, 0.952 mmole, 3 equivalents), Aliquat™ 336 (0.16 g, 0.405 mmole, 1.28equivalents), 2M sodium carbonate solution (5.4 mL, 10.8 mmole, 34equivalents) and 20 mL toluene. This was purged with a stream ofnitrogen for 30 min. Under a nitrogen purge,tetrakis(triphenylphosphine) palladium (0) (10 mg, 0.0068 mmole, 0.02equivalents) was added. The reaction mixture was then refluxed for 16hrs to give the borolane capped poly{(9-phenyl-9H-carbazole-3,6-diyl)[N,N′-bis(phenyl-4-yl)-N,N′-bis(4-butylphenyl)benzene-1,4-diamine]}(the borolane capped hole transport agent HT_(B) of Formula CVIII).

[0114] The molecular weight of the borolane capped poly{(9-phenyl-9H-carbazole-3,6-diyl)[N,N′-bis(phenyl-4-yl)-N,N′-bis(4-butylphenyl)benzene-1,4-diamine]}was verified in the following manner. A solution of 0.5 g bromobenzenein 5 mL nitrogen purged toluene was added followed by a further chargeof tetrakistriphenylphosphine palladium (0) (10 mg). The resultingmixture was refluxed for 16 hours, and then cooled to room temperature,and 30 mL water added. The organic layer was separated and washed withwater followed by brine. Precipitation into methanol, filtration andvacuum drying of the solid thus obtained gave 0.62 g of phenyl-cappedpoly{(9-phenyl-9H-carbazole-3,6-diyl)[N,N′-bis(phenyl-4-yl)-N,N′-bis(4-butylphenyl)benzene-1,4-diamine]}.Molecular weight determination by gel permeation chromatography versuspolystyrene standards gave Mw 2.39×10³, Mn 1.49×10³ and PD 1.67.

[0115] In step (1b) of Reaction Scheme I the bromide capped electrontransport oligomer ET_(A) of Formula CIX is prepared separately byreaction of 1,4-benzenediboronic acid bis(neopentyl glycol) cyclic esterwith a slight excess of2-(2,5-dibromophenyl)-5-[4-(octyloxy)phenyl]1,3,4-oxadiazole underSuzuki coupling conditions. The value of m can vary depending on theratio of borolane to bromide used, and in one example, the weightaverage molecular weight of the oligomer of Formula CIX is about 5,000.In step (2) of Reaction Scheme 1 the bromine capped electron transportoligomer ET_(A) of Formula CIX and the borolane capped hole transportagent HT_(B) of Formula CVIII are then reacted under Suzuki couplingconditions, followed by end capping with suitable end capping groups EC,in this case with phenyl, to give the HT-ET block copolymer of FormulaCX. The value of p can vary depending on the ratio of borolane tobromide used, and the weight average molecular weight of the copolymerof Formula CX can be in the range of about 5,000 to 1,000,000.

[0116] Reactive Monomers

[0117] In yet another broad aspect, this invention relates to novelintermediates useful for making polymeric arylenes, including thepresent electroactive polymeric arylenes. More specifically, thisinvention relates to polymerizable monomers having two reactive groups.More specifically, this invention relates to certain monomers having thestructure of Formula IV

[0118] wherein each D is a reactive group independently selected fromchlorine, bromine, iodine, boronic acid, and boronic ester; and whereina, E_(y) and Ar¹ are defined as in Formula I. Useful arylene groups andsubstitution patterns for —Ar¹(E_(y))_(a)- are selected from FormulasXI-XLIII described supra. In one embodiment —Ar¹(E_(y))_(a)- is selectedfrom Formulas CXI-CXIII.

[0119] wherein X is selected from —O—, —S—, and —N(R¹)—, and R¹, R², b,Ar², and R^(y) are as defined for Formulas XI-XLIII; and

[0120] wherein X is selected from —S— and —N(R1)—, R_(y) is as definedin Formulas XI-XLIII, and Ar² is a carbocyclic aryl group unsubstitutedor substituted with one or more substituents selected from fluoro, C₁₋₂₀fluoroalkyl, C₁₋₂₀ perfluoroalkyl, C₁₋₂₀ alkenyl, C₆₋₂₀ carbocyclicaryl, C₃₋₂₀ heteroaryl, C₁₋₃₀ hydrocarbyl containing one or more S, N,O, P, or Si atoms; C₃₋₂₀ alkyloxadiazolyl, C₃₋₃₀ aryloxadiazolyl, C₃₋₃₀alkyltriazolyl, and C₃₋₃₀ aryltriazolyl.

[0121] In another embodiment, useful reactive monomers of Formula IV areselected from compounds of Formulas CXVII, CXVIII, and CXIX

[0122] wherein D is chlorine, bromine, iodine, boronic acid, or boronicester, Q is phenylene or a bond, X is selected from —O—, —S—, and—N(R¹)—, R¹ is aryl, alkyl, heteroaryl, or heteroalkyl, each R³ is asdescribed in Formulas XXVII-XLIII, and each R^(z) when present is asdescribed in Formulas II and III.

[0123] Polymerizable difunctional electroactive arylene monomers of thepresent invention provide a means for incorporating effective amounts ofelectron transporting monomers into light emitting polymers, includingfluorene-containing polymers, without adversely affecting the emissioncharacteristics of the polymers.

[0124] Examples of useful reactive monomers comprising electroactivearylene units —Ar¹(E_(y))_(a)- include, but are not limited to thefollowing difunctional electroactive arylene Compounds 1-15:

[0125] The C₈H₁₇— groups in the above Compounds can be linear orbranched, for example, n-octyl, iso-octyl, and ethylhexyl.

[0126] Dihalogenated 1,3,4-oxadiazole monomers of Formula CXXII, whichare a subgenus of Formula IV and are of the type Halo-Ar¹(E_(y))-Halowhere Ar¹ is as defined in Formula I, E_(y) is Formula II, and Halo isbromo or chloro, can be synthesized by the acylation of substitutedtetrazoles as shown in Reaction Scheme II. In Reaction Scheme II, whereD¹ is Halo, and R^(z) is as defined above, a dihaloaroyl chloride ofFormula CXX is reacted with a substituted tetrazole of Formula CXXI withheating for about 12 hours in an inert solvent such as pyridine(Myznikov et al., J. Ge. Chem. of USSR, 62 (6), 1125-1128 (1992)) toform the dihalogenated oxadiazole monomer of Formula CXXII. Thetetrazole of Formula CXXI can be prepared by reaction of thecorresponding nitrile with NaN₃ and NH₄Cl in N,N-dimethylformamide (DMF)at reflux.

[0127] Alternatively, monomers of Formula CXXII can be prepared bycyclocondensation of benzoylaroylhydrazides as shown in Reaction SchemeIII (Grekow et al., J. Gen. Chem. USSR (Engl. Transl.), 30, 3763-3766(1960)) where D¹ and R^(z) are as defined above. In step (1a) ofReaction Scheme III, a dihaloaroyl hydrazide of Formula CXXIII isreacted with a substituted benzoylchloride of Formula CXXIV at roomtemperature in dichloromethane (DCM) with one equivalent oftriethylamine to form a benzoylaroylhydrazide of Formula CXXV.Alternatively, in step (1b) of Reaction Scheme III, a dihaloaroylchloride of Formula CXX is reacted with a substituted benzoyl hydrazidecompound of Formula CXXVI to form a benzoylaroylhydrazide of FormulaCXXV. In step (2) the benzoylaroylhydrazide of Formula CXXV is reactedwith phosphorus oxychloride at reflux to form the dihalogenatedoxadiazole monomer of Formula CXXII.

[0128] For example, electron transport monomers 1, 2, 3 and 10 were madeby condensation of the correponding 2,5-dihalobenzoyl chloride with theappropriately substituted benzoyl hydrazide.

[0129] 1,3-Dihalogenated monomers are similarly prepared. For example,the new electron transport monomers2-(3,5-dichlorophenyl)-5-[4-(octyloxy)phenyl]-1,3,4-oxadiazole (4) and2-(3,5-dibromophenyl)-5-[4-(octyloxy)phenyl]-1,3,4-oxadiazole (5) wereprepared by condensation of the corresponding 3,5-dihalobenzoyl chloridewith 4-octoxybenzoyl hydrazide, followed by cyclocondensation of theintermediate 3,5-dihalo-N′-[4-(octyloxy)benzoyl]-benzohydrazide.Monohalogenated 1,3,4-oxadiazole end capping group monomers weresimilarly prepared from the corresponding monohalogenated precursors asshown, for example, in Example 15.

[0130] Dihalogenated 1,3,4-thiadiazole monomers of Formula CXXVII, whichare subgenus of Formula IV can be prepared by cyclocondensation of thebenzoylaroylhydrazide intermediates as shown in Reaction Scheme IV (A.T. Prudchenko, J. Gen. Chem. USSR (Engl. Transl.), 37, 2082-2084(1967))where D¹ and R^(z) are as defined in Reaction Scheme II. In ReactionScheme IV the benzoylaroylhydrazide intermediate of Formula CXXV isreacted under metathesis conditions with P₂S₅ to provide the1,3,4-thiadiazoles of Formula CXXVII.

[0131] For example, the corresponding3-(2,5-dibromophenyl)-5-[4-(octyloxy)phenyl]-1,3,4-thiadiazole (9) maybe made in this way. Monohalogenated 1,3,4-thiadiazole end capping groupmonomers are similarly prepared from the corresponding monohalogenatedprecursors.

[0132] Dihalogenated 1,3,4-triazole monomers of Formula CXXVIII, whichare a subgenus of Formula IV, can be prepared by cyclocondensation ofthe benzoylaroylhydrazide intermediates as shown in Reaction Scheme V(E. Klingsberg, J. Org. Chem. 23, 1086(1958)) where D¹ and R^(z) are asdefined in Reaction Scheme II, and R¹ is aryl, alkyl, heteroaryl, orheteroalkyl. In step (1a) of Reaction Scheme V the benzoylaroylhydrazideintermediate of Formula CXXV is reacted with phosphorus trichloride atan elevated temperature, e.g., 150° C., in the presence of R¹NH₂,wherein R₁ is aryl or heteroaryl to provide the 1,3,4-triazole ofFormula CXXVIII. Alternatively, in step (1b) of Reaction Scheme V, thebenzoylaroylhydrazide is reacted with chlorine in glacial acetic acid(Moss et al., J. Chem. Soc. Perkin Trans. 1, 9,1999-2006 (1982)) orother non-reactive solvent to form the 1,4-dichloro-1,4-diphenylcompound of Formula CXXIX. In step (2b) of Reaction Scheme V, the1,4-dichloro-1,4-diphenyl compound of Formula CXXIX is reacted withR¹NH₂ (Gautun et al., Acta Chem. Scand. 45(6), 609-615 (1991)), whereinR₁ is alkyl or arylalkyl, to provide the corresponding 1,3,4-triazolesof Formula CXXVIII.

[0133] For example, the triazole derivative3-(2,5-dichlorophenyl)-4-(4-methoxyphenyl)-5-[4-(octyloxy)phenyl]-4H-1,2,4-triazole(8) was made by this method. Monohalogenated 1,3,4-triazole end cappinggroup monomers are similarly prepared from the correspondingmonohalogenated precursors.

[0134] Dihalogenated 1,3,4-oxadiazole monomers of Formula CXXX, whichare a subgenus of Formula IV and are of the type Halo-Ar¹(E_(y))-Halowhere Ar¹ is as defined in Formula I, E_(y) is Formula III, and Halo isbromo or chloro, can be synthesized by Suzuki coupling of amonofunctional diaryloxadiazole with a monoboronic acid/ester of thedihaloarylene as shown in Reaction Scheme VI. In Reaction Scheme VI,where R^(z) is as defined in Reaction Scheme II, 2,5-dichlorophenylboronic acid is reacted with a monofunctional2-(4-bromophenyl)-1,3,4-oxadiazole of Formula CXXXI in the presence ofpalladium bis(triphenylphosphine)dichloride and sodium carbonate in aninert solvent such as tetrahydrofuran with heat to form thedihalogenated 1,3,4-oxadiazole monomer of Formula CXXX. The2,5-dichlorophenyl boronic acid can be prepared by reacting1-bromo-2,5-dichlorobenzene with butyl lithium, then trimethyl boratefollowed by acidification.

[0135] For example, the new electron transport monomer2-(2′,5′-dichloro-1,1′-biphenyl-4-yl)-5-[4-(octyloxy)phenyl]-1,3,4-oxadiazole(6) can be prepared by reaction of 2,5-dichlorophenyl boronic acid with2-(4-bromophenyl)-5-[4-(octyloxy)phenyl]-1,3,4-oxadiazole under standardSuzuki coupling conditions. The corresponding 1,3,4-thiadiazole (4) maybe similarly prepared by reaction of 2,5-dichlorophenyl boronic acidwith 2-(bromophenyl)-5-[4-(octyloxy)phenyl]-1,3,4-thiadiazole understandard Suzuki coupling conditions. Also, the corresponding triazolecompound (7) may be similarly prepared by reaction of 2,5-dichlorophenylboronic acid with the monofunctional3-(4-bromophenyl)-4-(4-phenyl)-5-[4-(octyloxy)phenyl]-4H-1,2,4-triazoleintermediate. The dichloro monomers of Formula CXXX can be converted tothe corresponding dibromo monomers by a halogen exchange, for example,by reaction with hydrogen bromide in the presence of a catalytic amountof FeBr₃ (Yoon et al., J. Chem. Soc., Chem. Commun. 13, 1013-1014(1987).

[0136] In one useful embodiment of Formula IV, —Ar¹(E_(y))- is afluorenylene of Formulas XXXI-XXXIII. These can be made, for example,using the diaroylhydrazide cyclocondensation route according to ReactionScheme VII where R^(z) is as defined in Reaction Scheme II and where R³is independently in each case hydrogen, C₁₋₃₀ alkyl, C₁₋₃₀ alkenyl,C₆₋₂₀ aryl, C₃₋₂₀ heteroaryl, or C₁₋₃₀ hydrocarbyl containing one ormore S, N, O, P, or Si atoms. In step (1) of Reaction Scheme VII a2,7-dibromofluorene of Formula CXXXII is converted to the 4-methyl esterof Formula CXXXIII by reaction with methoxycarbonyl chloride in thepresence of aluminum chloride in an inert solvent such as carbondisulfide. In step (2), the 4-methyl ester of Formula CXXXIII isconverted to the hydrazide of Formula CXXXIV by reaction with hydrazinewith heating. In step (3) the hydrazide of Formula CXXXIV is convertedto the benzoylaroylhydrazide of Formula CXXXV by condensation with anunsubstituted or substituted benzoyl chloride of Formula CXXIV in thepresence of triethylamine. In step (4) the benzoylaroylhydrazide ofFormula CXXXV is cyclocondensed with phosphorus oxychloride at reflux toprovide the dibromofluorenyl-1,3,4-oxadiazole of Formula CXXXVI.

[0137] For example, the novel electron transport monomer2-(2,7-dibromo-9,9-dioctyl-9H-fluoren-4-yl)-5-[4-(octyloxy)phenyl]-1,3,4-oxadiazolecan be made by this method. In this case, 2,7-dibromo-9,9-disubstitutedfluorene monomer is converted to the 4-methyl ester (Bokova et al., J.Org. Chem. USSR (Engl.Transl.), 5, 1103-1106 (1969); Schidlo et al.,Chem Ber., 96, 2595-2600 (1963)), reacted with hydrazine, and thencondensed with 4-(octyloxy)benzoylchloride to give the 2,7-dibromo-N′-[4-(octyloxy)benzoyl]-fluorenoyl hydrazide intermediate which uponcyclocondensation gives the desired monomer.

[0138] The corresponding thiadiazole and triazole may be made byreaction of the intermediate benzoylaroylhydrazide of Formula CXXXV withP₂S₅ under metathesis conditions as in Reaction Scheme IV to provide the1,3,4-thiadiazole, and with R₁NH₂ as in Reaction Scheme V to provide the1,3,4-triazole.

[0139] In Reaction Scheme VIII below, monomers of Formula IV, wherein—Ar¹(E_(y))_(a)- is Formula XXXI, XXXII, or XXXIII, can also beconstructed through an Ulmann self coupling reaction in step (1) of aniodo-substituted benzoyloxy ester of Formula CXXXVII (wherein A is H,Cl, or Br and R′ is C₁₋₄ alkyl) with copper/bronze (see Rule et al., J.Chem. Soc. 1096-1101 (1937); Namkung et al., J. Med. Chem. Soc. 8,551-554 (1965)) followed by acid promoted ring closure in step (2) ofthe resulting diphenic acid of Formula CXXXVIII (Huntress et al., J. Am.Chem. Soc. 55, 4262-4270 (1933)), for example, with sulfuric acid at170° C., to give the 9-fluorenone of Formula CXXXIX. Reduction of the9-fluorenone with red phosphorus in step (3) provides the fluorene ofFormula CXL, which can be alkylated at the 9-position in step (4) byreaction with butyl lithium followed by an R³-halide or by phasetransfer methods utilizing, for example, benzyltriethylammonium chloridein dimethylsulfoxide, followed by 50% aqueous sodium hydroxide and thenR³-Br. Halogenation of the resulting 9-alkylated fluorene of FormulaCXLI, wherein A is H and R′ is methyl, at the 2 and 7 positions can bedone, for example, by reaction with chlorine in methyloxirane in step(5) to give the 2,7-dichloro fluorene of Formula CXLII, wherein R′ ismethyl (Schidlo et al., Chem Ber. 2595-2600 (1963)). Treatment of the2,7-dichloro fluorene of Formula CXLII with thionyl chloride in step (6)gives the reactive acyl chloride intermediate of Formula CXLIII. Theoxadiazole, thiadiazole, or triazole may then be formed at the acylchloride group of the acyl chloride intermediate via a benzohydrazideintermediate as in Reaction Schemes III-V or by direct coupling with atetrazole as in Reaction Scheme II.

[0140] The novel electron transport monomer2-[4-(2′,7′-dichloro-9′,9′-dioctyl-9′H-fluoren-4′-yl)phenyl]-5-[4-(octyloxy)phenyl]-1,3,4-oxadiazole(15)

[0141] can be prepared by monobromination of2,7-dichloro-9,9-dioctyl-9H-fluorene to give4-bromo-2,7-dichloro-9,9-dioctyl-9H-fluorene, conversion to thecorresponding dichloroboralane followed by reaction with2-(4-bromophenyl)-5-[4-(octyloxy)phenyl]-1,3,4-oxadiazole under standardSuzuki coupling conditions.

[0142] Monomers of Formula IV, wherein —Ar¹(E_(y))_(a)- is a9,10-dihydrophenanthrene of Formula XXVII, XXVIII, or XXIX can besynthesized by the process shown in Reaction Scheme IX below. In step(1), Suzuki coupling of the phenylborolane of Formula CXLV with themethyl cyanobromobenzoate of Formula CXLIV provides the cyanodiphenicester of Formula CXLVI. In step (2), acyloin reduction (Fritsch et al.,Chem Ber. 125, 849-855 (1992) can provide thecyano-9,10-dihydrophenanthrene of Formula CXLVII. In step (3),dibromination with bromine, for example, in methylene choride at roomtemperature, of CXLVII provides thedibromo-cyano-9,10-dihydrophenanthrene of Formula CXLVIII, the cyanogroup of which can be converted to a carboxylic acid group by treatmentwith base or to a tetrazole group by treatment with NaN₃ and NH₄Cl inDMF at reflux. An oxadiazolyl, thiadiazolyl, or triazolyl group can beformed from the carboxylic acid group by first halogenation with thionylchloride or chlorine in methyloxirane, followed by formation of theoxadiazole, thiadiazole, or triazole group as in Reaction Schemes III,IV, or V. The tetrazole can be reacted with an aryloyl chloride as shownin Reaction Scheme II to form an oxadiazole.

[0143] Monomers of Formula IV, wherein —Ar¹(E_(y))_(a)- is Formula XXXV,XXXVI, XXXVII, or XXXVIII may be made as illustrated by the preparationof a 2,8-dibromo-6,12-dihydroindeno[1,2-b]fluorene using the process ofReaction Scheme X. In step (1), Suzuki coupling of2-(2,5-dimethylphenyl)-4,4,5,5-tetramethyl [1,3,2]dioxaborolane withcommercially available 2-bromo-9-fluorenone provides2-(2,5-dimethylphenyl)fluoren-9-one. Commercially available2-bromo-p-xylene is converted to2-(2,5-dimethylphenyl)-4,4,5,5-tetramethyl[1,3,2]dioxaborolane bytreatment with butyl lithium and reaction of the lithiated intermediatewith 2-isopropoxy-4,4,5,5-tetramethyl[1,3,2]dioxaborolane. In step (2),2-(2,5-dimethylphenyl)fluoren-9-one can be converted to2-bromo-7-(4-bromo-2,5-dimethylphenyl)fluoren-9-one with bromine inchloroform at 0° C. Regiospecific bromination at the 4′-position of thephenyl ring is directed by the 5′-methyl and fluorene substituents. Instep (3), 2-bromo-7-(4-bromo-2,5-dimethylphenyl)fluoren-9-one canundergo potassium permanganate oxidation to provide2-bromo-5-(7-bromo-9-oxo-9H-fluoren-2-yl)-terephthalic acid. Ringclosure, in step-(4), to2,8-dibromo-6,12-dioxa-6,12-dihydroindeno[1,2-b]fluorene-3-carboxylicacid is effected by treatment with sulfuric acid. Reduction of2,8-dibromo-6,12-dioxa-6,12-dihydroindeno[1,2-b]fluorene-3-carboxylicacid, in step (5), with red phosphorus provides2,8-dibromo-6,12-dihydroindeno[1,2-b]fluorene-3-carboxylic acid. In step(6), alkylated by reaction with butyl lithium followed by an R³-halideor by phase transfer methods utilizing, for example,benzyltriethylammonium chloride in dimethylsulfoxide, followed by 50%aqueous sodium hydroxide and then R³—Br provides theindeno[1,2-b]fluorene derivative of Formula CXLIX. Treatment of theindeno[1,2-b]fluorene of Formula CXLIX with thionyl chloride gives thereactive acyl chloride intermediate of Formula CL. The oxadiazole,thiadiazole, or triazole may be formed at the acyl chloride group of theacyl chloride intermediate via a benzhydrazide intermediate as inReaction Schemes III-V or by direct coupling with a tetrazole as inReaction Scheme II. In step (8), for example, the oxadiazole of FormulaCLI is provided by reaction of the acyl chloride intermediate of FormulaCL with 5-(4-octyloxyphenyl)-1H-tetrazole as in Reaction Scheme II.

[0144] Monomers of Formula IV, wherein —Ar¹(E_(y))_(a)- is Formula XLIIIwith one or both terminal rings substituted with E_(y), may be made byfirst making a dicarboxylic acid of3,10-dibromo-5,6,12,13-tetrahydrodibenzo[a,h]anthracene as illustratedin Reaction Scheme XI, below. In step (1), dimethyl2,4-dibromoterephthalate (available from Maybridge Chemical Co., UK) isreacted with the cyanophenylborolane of Formula CLII (see Kristensen etal., Org. Lett. 10, 1435-1438 (2001)) to provide the cyano substitutedtriphenyl compound of Formula CLIII. Acyloin reduction (see Fritsch etal., Chem Ber. 125, 849-855 (1992)) of the compound of Formula CLIII, instep (2), can give the dicyano substituted5,6,12,13-tetrahydrodibenzo[a,h]anthracene of Formula CLIV.Dibromination, for example, with bromine in chloroform at 0° C., in step(3), can provide the dicyano substituted3,10-dibromo-5,6,12,13-tetrahydrodibenzo[a,h]anthracene of Formula CLV.Treatment of the compound of Formula CLV, in step (4), with base cangive the dicarboxylic acid of Formula CLVI. In step (5), treatment ofthe compound of Formula CLVI with thionyl chloride can give the reactiveacyl chloride intermediate of Formula CLVII.

[0145] The oxadiazole, thiadiazole, or triazole may be formed at theacyl chloride groups of the acyl chloride intermediate of Formula CLVIIvia a benzoylaroylhydrazide intermediate as in Reaction Schemes III-V orby direct coupling with a tetrazole as in Reaction Scheme II.

[0146] As an alternative, the cyano groups of the dicyano substituted3,10-dibromo-5,6,12,13-tetrahydrobenzo[a,h]anthracene or Formula CLV canbe converted to tetrazole groups by treatment with NaN₃ and NH₄Cl in DMFat reflux. The tetrazole can be reacted with an aryloyl chloride asshown in Reaction Scheme II to form an oxadiazole.

[0147] The monocyano substituted5,6,12,13-tetrahydrodibenzo[a,h]anthracene of Formula CLVIII can be madethrough a sequential Suzuki coupling shown in Reaction Scheme XII. Instep (1), the phenylborolane of Formula CLIX is reacted with excess(typically 5 equivalents) dimethyl 2,4-dibromoterephthalate to give the4-bromobiphenyl of Formula CLX as the major product. In step (2), afterpurification, the 4-bromobiphenyl of Formula CLX is reacted with thecyanophenylborolane of Formula CLII under similar Suzuki couplingconditions to give the monocyano substituted triphenyl of Formula CLXI.In step (3), acyloin reduction as in Reaction Scheme XI provides themonocyano substituted 5,6,12,13-tetrahydrodibenzo[a,h]anthracene ofFormula CLVIII. Subsequent dibromination, for example, with bromine inchloroform at 0° C., in step (4), may give the dibromo monocyanocompound of Formula CLXII. The dibromo monocyano compound of FormulaCLXII may be reacted with with NaN₃ and NH₄Cl in DMF at reflux, in step(5), to form the tetrazole of Formula CLXIII, which can be reacted withan aroyl chloride, Ar²C(O)Cl, in step (6) to form the5,6,12,13-tetrahydrodibenzo[a,h]anthracene bearing a pendant oxadiazoleof Formula CLXIV. Alternatively, the cyano group on the compound ofFormula CLXII can be hydrolyzed to form the carboxylic acid, which canin turn be treated with thionyl chloride to form the acyl chlorideintermediate. The acyl chloride intermediate maybe reacted with an aroylhydrazide as in Reaction Scheme III to form a benzoylaroylhydrazide,which can be converted to an oxadiazole, thiadiazole, or triazole asdescribed in Reaction Schemes III-V, providing monomers of Formula IV,wherein —Ar¹(E_(y))_(a)- is Formula XLIII with one terminal ringsubstituted with E_(y).

[0148] The dihalo monomers prepared as described in the above reactionschemes can be converted to the corresponding diborolane by treatmentwith bis(pinacolato)diboron and potassium acetate catalyzed by[1,1′-bis(diphenylphosphino)ferrocene]dichloropalladium in dimethylsulfoxide (Meng et al., J. Am. Chem. Soc. 123(37), 9214-9215 (2001)) togive 10 the diborolane derivative.

[0149] Electroactive Compositions

[0150] In another broad aspect, this invention provides electroactivecompositions comprising an electroactive polymeric arylene of theinvention.

[0151] There is a need in the art for solution processibleelectroluminescent compositions that can be uniformly coated or printedonto a substrate for the purpose of fabricating OLED devices. All thecomponents of a solution processible composition are soluble in a commonsolvent or mixture of solvents, and the solution processible compositioncan be coated onto a substrate to form a continuous film, preferablyfree of pin holes. OLED devices prepared from these compositionspreferably should provide low operating voltages, high external quantumefficiencies, proper color coordinates (e.g. red, green and blue fordisplay applications, white for backlight applications), long operatinglifetimes, and compatibility with the printing process (e.g. inkjetprinting, thermal induced laser imaging, gravure printing, etc).

[0152] One particularly attractive approach has been to prepare blendsof small molecule agents (hole transport agent, electron transportagent, and emissive molecular dopant) in an inert polymeric matrix suchas polystyrene. This is referred to as a molecularly doped polymercomposition. Such compositions are solution processible. However, theinert matrix does little to assist in the transport of charge carriers,leading to higher operating voltages and shorter device lifetimes. Thevoltage can be decreased by employing a charge carrier in the polymerhost. For example, polyvinyl carbazole (a p-type, or hole transportingpolymer) can be used as a host for molecular electron transportmaterials and emissive dopants to fabricate electroluminescent deviceswith lower operating voltages.

[0153] Low molecular weight emitting materials tend to be p-type (thatis, they preferentially transport holes) due to their low electronaffinities, which means that they require n-type electron-transportcompanions or companion layers in electroluminescent devices in order toshow luminescence. There has been a shortage in the art of n-typeelectron transport polymers to serve as solution processible hostmaterials for making blended emissive organic elements. The desiredfeatures of electron transport materials are (i) large electron affinityand high electron mobility for efficient injection and transport ofelectrons, and (ii) large band gap in order to prevent energy transferof excitons, which are produced by charge recombination within theelectroluminescent species, or from the electroluminescent species tothe electron transport material.

[0154] In one useful embodiment, the electroactive composition is anelectroluminescent composition comprising an electroactive polymericarylene of the invention; said composition optionally includes othermaterials, such as, for example, hole transport material, electrontransport material, binder, polymeric binder, molecular emitters, lightemitting polymers (LEP's), waveguiding particles, phosphorescentcompounds, and color conversion materials.

[0155] One embodiment relates to blends of two or more of thehomopolymers or copolymers of the invention without limits on relativeproportions of the individual components. Such blends may be prepared bysolution blending, or blending in the melt state.

[0156] A second embodiment relates to blends containing at least 0.1weight % of at least one electroactive polymeric arylene (homopolymer orcopolymer) of the invention with a material selected from anotherelectroactive polymer, an electroactive small molecule, an inert polymerbinder, and combinations thereof. Such blends may be prepared bysolution blending, or blending in the melt state.

[0157] These compositions can be useful for making organic electronicdevices by thermal patterning of the materials onto a receptor. They canalso be useful for non-thermal printing, patterning, and transfermethods including, for example, inkjet printing, screen printing, andphotolithographic patterning.

[0158] Hole transport materials include hole transport monomers andpolymers. Hole transport monomers useful in these blended systems arepreferably selected from tertiary aromatic amine derivatives as definedabove, electron rich heteroarylene derivatives as defined above,electron rich inorganic and organometallic complexes. Other examplesinclude copper phthalocyanine (CuPC); and other compounds such as thosedescribed in H. Fujikawa et al., Synthetic Metals, 91, 161 (1997) and J.V. Grazulevicius, P. Strohriegl, “Charge-Transporting Polymers andMolecular Glasses”, Handbook of Advanced Electronic and PhotonicMaterials and Devices, H. S. Nalwa (ed.), 10, 233-274 (2001), both ofwhich are incorporated herein by reference.

[0159] Hole transport polymers useful in these blends include polymersderived from the hole transport monomers mentioned above, polyvinylcarbazoles, and triaryl amine based polymers of the types taught in DE3610649,U.S. Pat. No. 5,681,664, WO 9932537 and WO 9806773, all of whichare incorporated herein by reference.

[0160] Electron transport materials include electron transport monomersand polymers. Electron transport monomers useful in these blends arepreferably selected from condensed polycyclic arylenes as defined above,heteroaromatic compounds comprising imine linkages as defined above, andelectron deficient inorganic complexes. Exemplary electron transportmonomers include oxadiazoles such as2-(4-biphenyl)-5-(4-t-butylphenyl)-1,3,4-oxadiazole (also known as PBD)and 1,3-bis[5-(4-(1,1-dimethylethyl)phenyl)-1,3,4-oxadiazol-2-yl]benzene(known as PBD dimer) as well as starburst and dendrimeric derivatives ofoxadiazoles (Bettenbhausen et al., Synthetic Metals, 91, 223 (1997));N-substituted triazole derivatives such as3-(4-biphenylyl)-4-phenyl-5-(4-tert-butylphenyl)1,2,4-triazole (alsoknown as TAZ) as well as starburst and dendrimeric derivatives oftriazoles; organometallic compounds such as tris(8-hydroxyquinolato)aluminum (Alq₃) and biphenylatobis(8-hydroxyquinolato)aluminum (BAlq);and other compounds described in C. H. Chen, et al., Macromol. Symp.125, 1 (1997) and J. V. Grazulevicius, P. Strohriegl,“Charge-Transporting Polymers and Molecular Glasses”, Handbook ofAdvanced Electronic and Photonic Materials and Devices, H. S. Nalwa(ed.), 10, 233 (2001), both of which are incorporated herein byreference.

[0161] Molecular emitters useful in these blends are preferably selectedfrom, but not limited to, molecular emitters derived from fluorescentpolynuclear carbocyclic arylene and heteroarylene derivatives,phosphorescent cyclometallated chelate complexes of Ir(III), Rh(III),Os(II), Ru(II), Ni(II) and Pt(II), and fluorescent chelate complexes ofZn(II) and Al(III). Examples of useful fluorescent polynuclearcarbocyclic arylene emitters include molecules derived from perylene,benzo[g,h,i]perylene, anthracene, pyrene, decacyclene and fluorenes.Examples of useful fluorescent polynuclear heteroarylene derivativesinclude molecules derived from coumarins such as10-(2-benzothiazolyl)-2,3,6,7-tetrahydro-1,1,7,7-tetramethyl-1H,5H,11H-[1]benzopyrano[6,7,8-i,j]quinolizin-11-one (also known as CoumarinC545T), 3-(2-benzothiazolyl)-7-diethylaminocoumarin (also known asCoumarin 6 or Coumarin 540), and 3-thiophenyl-7-methoxycoumarin.Examples of useful phosphorescent cyclometallated chelate complexes ofIr(III), Rh(III), Os(II), Ru(II), and Pt(II) include molecules derivedfrom phosphorescent organometallic L¹ ₃Ir (III), L¹ ₃Rh (III),L¹L²Ir(III)X, L¹L²Rh(III)X, L¹L²Os(II)Y, L¹L²Ru(II)Y, L¹L²Pt(II)compounds where L¹ and L² can be the same or different in each instanceand are optionally substituted cyclometallated bidentate ligands of2-(1-naphthyl)benzoxazole, 2-phenylbenzoxazole, 2-phenylbenzothiazole,2-phenylbenzimidazole, 7,8-benzoquinoline, coumarin, phenylpyridine,benzothienylpyridine, 3-methoxy-2-phenylpyridine, thienylpyridine,tolylpyridine; X is selected from the group consisting ofacetylacetonate (“acac”), hexafluoroacetylacetonate, salicylidene,picolinate, and 8-hydroxyquinolinate; Y is selected from charge neutralchelating compounds such as optionally substituted derivatives ofphenathroline or bipyridine. Useful cyclometallated Ir(III) chelatederivatives include those taught in WO 0070655 and WO 0141512 A1, bothincorporated herein by reference, and useful cylcometallated Os(II)chelate derivatives include those taught in U.S. Ser. No. 09/935,183filed Aug. 22, 2001, incorporated herein by reference. Platinum(II)porphyrins such as octaethyl porphyrin (also known as Pt(OEP)) are alsouseful. Examples of useful fluorescent chelate complexes of Zn(II) andAl (III) include complexes such as bis(8-quinolinolato) zinc(II),bis(2-(2-hydroxyphenyl)benzoxazolate) zinc(II),bis(2-(2-hydroxyphenyl)benzothiazolate) zinc(II),bis(2-(2-hydroxyphenyl)-5-phenyl-1,3,4-oxadiazole) zinc(II),bis(8-quinolinolato) aluminum(III), andbiphenylatobis(8-hydroxyquinolato)aluminum (BAlq). Useful fluorescent Zn(II) chelates include those taught by Tokito et al., Synthetic Metals,111-112, 393-396 (2000) and in WO 01/39234 A2, incorporated herein byreference. Useful Al(III) chelates include those taught in U.S. Pat. No.6,203,933 B1, incorporated herein by reference.

[0162] Examples of LEPs for use in these blends are polymers andcopolymers of the polyfluorenes (PFs), polyparaphenylenes (PPPs), andpolyphenylenevinylenes (PPVs).

[0163] In one particularly useful embodiment, the electroactivepolymeric arylene (homopolymer or copolymer) of the invention is blendedwith one or more materials selected from hole transport polymers, holetransport monomers, electron transport monomers, and inert polymerbinders to provide a composition that supports transport of both holesand electrons. Optionally, this film is charge balanced by virtue of theblend ratio and components. Optionally, a light emitting polymer ormolecular emitter is added to the blend to form a solution processiblecomposition that can be formed into a light emitting element. Oneexemplary composition for this type of blend comprises (1) a homopolymerof Formula V or a copolymer of Formulas VI-VIII wherein greater than 25%of the monomer units in the electroactive polymeric arylene are aryleneunits —Ar¹(E_(y))_(a)- and at least 90% of the remaining monomer unitsare independently phenylene group arylene units or naphthalene grouparylene units, (2) one or more hole transport monomers, preferablyderived from the class of tertiary aromatic amines, in an amount that is5% -50% by weight with respect to the polymer, and (3) one or moremolecular emitters in an amount that is 0.05-10% by weight with respectto the polymer. The molecular weight of the host polymer is preferablyin the range of Mw=2,000 to 100,000, more preferably in the range ofMw=3,000-50,000, even more preferably in the range of Mw=5,000-30,000.Exemplary molecular emitters include derivatives of perylene,benzo[g,h,i]perylene, t-butylated decacyclene, platinum (II) porphyrins,coumarins, styryl dyes, 8-quinolinolato zinc(II) complexes,8-quinolinolato aluminum (III) complexes, and cyclometallated iridium(III) chelate derivatives. One exemplary host electroactive polymericarylene is a homopolymer of Formula V wherein X═O and Ar¹ is phenyleneor fluorenylene. Another exemplary host polymer is a copolymer ofFormulas VI-VIII wherein Ar¹ is phenylene or fluorenylene and Ar³ andAr⁴ are derived from phenylene or fluorenylene.

[0164] These types of compositions are solution processible, can be spincoated to provide thin films that are electroluminescent, can bethermally imaged to form pixilated arrays useful in OLED displaymanufacture, and can be optimized to give rise to high quantumefficiency electroluminescence by varying the thickness of the film andthe ratio of components within the ranges specified. Operating voltagesare significantly reduced relative to control lamps prepared byreplacing the electroactive polymeric arylene host with a correspondingamount of polystyrene and a molecular electron transport agent of thesame general structure as Ar¹-(E_(y))_(a). The emission color can bevaried by choice of the emitter. For example, perylene, Zn(ODZ)₂, or3-thienyl-7-methoxy-coumarin give rise to blue emission,Ir(bthpy)₂(acac) or platinum octaethylporphyrin gives rise to redemission, Coumarin 6, Coumarin C545T and Ir(ppy)₃ give rise to greenemission, t-butylated decacyclene gives rise to white emission. In thecase of electroluminescent host electroactive polymeric arylenes,especially those comprising fluorene monomer units, emission from boththe polymer and from the molecular emitter can be achieved (e.g. blueemission from the polymer, green emission from the emitter). Thisprovides a way to generate a white emissive film for backlightapplications.

[0165] In a second particularly useful embodiment, an electroluminescentcopolymer of the invention is blended with one or more materialsselected from hole transport polymers, hole transport monomers, orelectron transport monomers, and inert polymer binders to provide asolution processible composition that supports transport of both holesand electrons and can be formed into a light emitting element.Optionally, this film is charge balanced by virtue of the blend ratioand components. Optionally, a second light emitting polymer or amolecular emitter is added to the blend to form a modified lightemitting composition. One exemplary composition for this type of blendcomprises (1) less than 50% by weight, more preferably less than 25% byweight, based on the weight of the composition, of a copolymer ofFormulas VI-VIII wherein 5-75% of the monomer units are electroactivearylene units Ar¹-(E_(y))_(a) and the polymer is electroluminescent byvirtue of the choice of Ar¹ and the comonomers Ar³ and Ar⁴, (2) one ormore hole transport monomers, preferably derived from the class oftertiary aromatic amines, and (3) one or more electron transportmonomers, preferably derived from the class of heteroaryl compoundshaving imine linkages. These compositions are solution processible, canbe spin coated to provide thin films that are electroluminescent, can bethermally imaged to form pixilated arrays useful in OLED displaymanufacture, and can be optimized to give rise to high quantumefficiency electroluminescence by varying the thickness of the film andthe ratio of components within the ranges specified. Electroluminescenceof these compositions derives principally from the light emittingpolymer of Formula VI-VIII.

[0166] For this type of composition, the blending of the polymer withhole and electron transport monomers improves thermal transfercharacteristics relative to the neat polymer. Incorporation ofelectroactive arylene units —Ar¹(E_(y))_(a)- into the polymer structureimproves the efficiency for migration of charge carriers onto thepolymer from the molecular host comprised of hole and electron transportmonomers, when compared with blending of a corresponding light emittingpolymer that does not comprise the —Ar¹(E_(y))_(a)-. This has the effectof decreasing background current and exciton formation in the molecularhost, while increasing the efficiency for exciton recombination on theemissive polymer. The emission color can be varied by choice of Ar¹,Ar³, and Ar⁴ in Formulas VI-VIII.

[0167] Organic Electronic Devices

[0168] In another broad aspect, the present invention provides organicelectronic devices comprising one or both of the electroactive polymericarylenes and electroactive compositions of the present invention.

[0169] Organic electronic devices are articles that include layers oforganic materials, at least one of which can conduct an electriccurrent. Examples of organic electronic devices that can be made usingthe polymers and electroactive compositions of this invention includeorganic transistors, photovoltaic devices, organic electroluminescent(OEL) devices such as organic light emitting diodes (OLEDs), and thelike.

[0170] In one embodiment, this invention provides organicelectroluminescent devices that comprise one or both of theelectroactive polymeric arylenes and electroactive compositions of thepresent invention; wherein one or both are electroluminescent.

[0171] Organic electroluminescent (OEL) display or device refers toelectroluminescent displays or devices that include an organic emissivematerial, whether that emissive material includes a molecular emitter, asmall molecule (SM) doped polymer, a light emitting polymer (LEP), adoped LEP, a blended LEP, or another organic emissive material whetherprovided alone or in combination with any other organic or inorganicmaterials that are functional or non-functional in the OEL display ordevices. OLEDs have potential use in applications such as backlightingof graphics, pixelated displays, and large emissive graphics.

[0172] In at least some instances, an OEL device includes one or morelayers, of one or more suitable organic materials, referred to as theorganic emissive element, sandwiched between a cathode and an anode. Theemissive element must be capable of electron transport and holetransport as well as light emission. When activated, electrons areinjected into the organic layer(s) from the cathode and holes areinjected into the organic layer(s) from the anode. Electrons reside inthe emissive element as radical anions and holes as radical cations. Asthe injected charges migrate towards the oppositely charged electrodes,they may recombine to form electron-hole pairs which are typicallyreferred to as excitons. The region of the device in which the exitonsare generally formed can be referred to as the recombination zone. Theseexcitons, or excited state species, can emit energy in the form of lightas they decay back to a ground state.

[0173] A light emitting layer in the emissive element includes a lightemitting polymer or a molecular emitter and optionally includes othermaterials, such as, for example, hole transport material, electrontransport material, binder, polymeric binder, waveguiding particles,phosphorescent compounds, and color conversion materials.

[0174] Electroluminescent polymers and electroluminescent compositionsof this invention are particularly useful as organic emissive elementsin OEL devices because they provide a high quantum efficiency and longservice life from a solution processible and thermally printablecomposition.

[0175] Other layers can also be present in OEL devices such as holetransport layers, electron transport layers, hole injection layer,electron injection layers, hole blocking layers, electron blockinglayers, buffer layers, and the like. In addition, photoluminescentmaterials can be present in the electroluminescent layer or other layersin OEL devices, for example, to convert the color of light emitted bythe electroluminescent material to another color. These and other suchlayers and materials can be used to alter or tune the electronicproperties and behavior of the layered OEL device, for example toachieve a desired current/voltage response, a desired device efficiency,a desired color, a desired brightness, and the like.

[0176] Electroactive polymeric arylenes of the present invention canalso be particularly useful as a hole blocking layer and an electrontransport layer in OEL devices.

[0177] A typical anode is indium-tin-oxide (ITO) sputtered onto atransparent substrate such as plastic or glass. Suitable OLED substratesinclude glass, transparent plastics such as polyolefins,polyethersulfones, polycarbonates, polyesters, polyarylates, andpolymeric multilayer films, ITO coated barrier films such as the PlasticFilm Conductor available from 3M Optical Systems Division (3M, St. Paul,Minn.), surface-treated films, and selected polyimides. It is highlydesirable that the OLED substrate has barrier properties matching thoseof the protective (or counter electrode) film. Flexible rolls of glassmay also be used. Such a material may be laminated to a polymer carrierfor better structural integrity.

[0178] The anode material coating the substrate is electricallyconductive and may be optically transparent or semi-transparent. Inaddition to ITO, suitable anode materials include indium oxide, fluorinetin oxide (FTO), zinc oxide, vanadium oxide, zinc-tin oxide, gold,platinum, palladium silver, other high work function metals, andcombinations thereof.

[0179] In practice, the anode is optionally coated with 10-200 Å of anionically conducting polymer such as PEDT or PANI to help planarize thesurface and to modify the effective work function of the anode.

[0180] Typical cathodes include low work function metals such asaluminum, barium, calcium, samarium, magnesium, silver, magnesium/silveralloys, lithium, lithium fluoride, ytterbium, and alloys of calcium andmagnesium.

[0181] As one embodiment of a device structure, FIG. 1 illustrates anOEL display or device 100 that includes a device layer 110, whichincludes the electroactive polymeric arylene of the present invention,and a substrate 120. Any other suitable display component can also beincluded with display 100. Optionally, additional optical elements orother devices suitable for use with electronic displays, devices, orlamps can be provided between display 100 and viewer position 140 asindicated by optional element 130.

[0182] In some embodiments like the one shown, device layer 110 includesone or more OEL devices that emit light through the substrate toward aviewer position 140. The viewer position 140 is used generically toindicate an intended destination for the emitted light whether it be anactual human observer, a screen, an optical component, an electronicdevice, or the like. In other embodiments (not shown), device layer 110is positioned between substrate 120 and the viewer position 140. Thedevice configuration shown in FIG. 1 (termed “bottom emitting”) may beused when substrate 120 is transmissive to light emitted by device layer110 and when a transparent conductive electrode is disposed in thedevice between the emissive layer of the device and the substrate. Theinverted configuration (termed “top emitting”) may be used whensubstrate 120 does or does not transmit the light emitted by the devicelayer and the electrode disposed between the substrate and the lightemitting layer of the device does not transmit the light emitted by thedevice.

[0183] Device layer 110 can include one or more OEL devices or elements,for example, organic light emitting diodes, arranged in any suitablemanner. For example, in lamp applications (e.g., backlights for liquidcrystal display (LCD) modules), device layer 110 might constitute asingle OEL device that spans an entire intended backlight area.Alternatively, in other lamp applications, device layer 110 mightconstitute a plurality of closely spaced OEL elements that can becontemporaneously activated. For example, relatively small and closelyspaced red, green, and blue light emitters can be patterned betweencommon electrodes so that device layer 110 appears to emit white lightwhen the emitters are activated. Other arrangements for backlightapplications are also contemplated.

[0184] In direct view or other display applications, it may be desirablefor device layer 110 to include a plurality of independently addressableOEL devices or elements that emit the same or different colors. Eachdevice might represent a separate pixel or a separate sub-pixel of apixilated display (e.g., high resolution display), a separate segment orsub-segment of a segmented display (e.g., low information contentdisplay), or a separate icon, portion of an icon, or lamp for an icon(e.g., indicator applications).

[0185] Referring back to FIG. 1, device layer 110 is disposed onsubstrate 120. Substrate 120 can be any substrate suitable for OELdevice and display applications. For example, substrate 120 can compriseglass, clear plastic, or other suitable material(s) that aresubstantially transparent to visible light. Substrate 120 can also beopaque to visible light, for example stainless steel, crystallinesilicon, poly-silicon, or the like. Because some materials in OELdevices can be particularly susceptible to damage due to exposure tooxygen or water, substrate 120 preferably provides an adequateenvironmental barrier, or is supplied with one or more layers, coatings,or laminates that provide an adequate environmental barrier.

[0186] Substrate 120 can also include any number of devices orcomponents suitable in OEL devices and displays such as transistorarrays and other electronic devices; color filters, polarizers, waveplates, diffusers, and other optical devices; insulators, barrier ribs,black matrix, mask work and other such components; and the like.Generally, one or more electrodes will be coated, deposited, patterned,or otherwise disposed on substrate 120 before forming the remaininglayer or layers of the OEL device or devices of the device layer 110.When a light transmissive substrate 120 is used and the OEL device ordevices are bottom emitting, the electrode or electrodes that aredisposed between the substrate 120 and the emissive material(s) arepreferably substantially transparent to light, for example transparentconductive electrodes such as indium tin oxide (ITO) or any of a numberof other transparent conductive oxides.

[0187] Element 130 can be any element or combination of elementssuitable for use with OEL display or device 100. For example, element130 can be an LCD module when device 100 is a backlight. One or morepolarizers or other elements can be provided between the LCD module andthe backlight device 100, for instance an absorbing or reflectiveclean-up polarizer. Alternatively, when device 100 is itself aninformation display, element 130 can include one or more of polarizers,wave plates, touch panels, antireflective coatings, anti-smudgecoatings, projection screens, brightness enhancement films, or otheroptical components, coatings, user interface devices, or the like.

[0188]FIGS. 4A to 4D illustrate examples of different OEL device (forexample, an organic light emitting diode) configurations of the presentinvention. Each configuration includes a substrate 250, an anode 252, acathode 254, and a light emitting layer 256, which can include anelectroactive polymeric arylene of the present invention. Theconfigurations of FIGS. 4C and 4D also include a hole transport layer258 and the configurations of FIGS. 4B and 4D include an electrontransport layer 260, which can include an electroactive polymericarylene of the present invention. These layers conduct holes from theanode or electrons from the cathode, respectively. The OEL device ofFIG. 4A includes an electroactive polymeric arylene in the lightemitting layer 256. The OEL devices of FIGS. 4B-4D include anelectroactive polymeric arylene in one or both of the light emittinglayer 256 or the electron transport layer 260.

[0189] The anode 252 and cathode 254 are typically formed usingconducting materials such as metals, alloys, metallic compounds, metaloxides, conductive ceramics, conductive dispersions, and conductivepolymers, including, for example, gold, platinum, palladium, aluminum,calcium, titanium, titanium nitride, indium tin oxide (ITO), fluorinetin oxide (FTO), and polyaniline. The anode 252 and the cathode 254 canbe single layers of conducting materials or they can include multiplelayers. For example, an anode or a cathode may include a layer ofaluminum and a layer of gold, a layer of calcium and a layer ofaluminum, a layer of aluminum and a layer of lithium fluoride, or ametal layer and a conductive organic layer.

[0190] The hole transport layer 258 facilitates the injection of holesfrom the anode into the device and their migration towards therecombination zone. The hole transport layer 258 can further act as abarrier for the passage of electrons to the anode 252. The holetransport layer 258 can include, for example, a diamine derivative, suchas N,N′-bis(3-methylphenyl)-N,N′-bis(phenyl)benzidine (also known asTPD) or N,N′-bis(3-naphthalen-2-yl)-N,N′-bis(phenyl)benzidine (NPB), ora triarylamine derivative, such as,4,4′,4″-Tris(N,N-diphenylamino)triphenylamine (TDATA) or4,4′,4″-Tris(N-3-methylphenyl-N-phenylamino)triphenylamine (mTDATA).Other examples include copper phthalocyanine (CuPC);1,3,5-Tris(4-diphenylaminophenyl)benzenes (TDAPBs); and other compoundssuch as those described in H. Fujikawa, et al., Synthetic Metals, 91,161 (1997) and J. V. Grazulevicius, P. Strohriegl, “Charge-TransportingPolymers and Molecular Glasses”, Handbook of Advanced Electronic andPhotonic Materials and Devices, H. S. Nalwa (ed.), 10, 233-274 (2001),both of which are incorporated herein by reference.

[0191] The electron transport layer 260 facilitates the injection ofelectrons and their migration towards the recombination zone. Theelectron transport layer 260, which can include an electroactivepolymeric arylene of the present invention, can further act as a barrierfor the passage of holes to the cathode 254, if desired. In someexamples, the electron transport layer 260 can be formed using theorganometallic compound tris(8-hydroxyquinolato) aluminum (Alq3). Otherexamples of electron transport materials useful in electron transportlayer 260 include1,3-bis[5-(4-(1,1-dimethylethyl)phenyl)-1,3,4-oxadiazol-2-yl]benzene,2-(biphenyl-4-yl)-5-(4-(1,1-dimethylethyl)phenyl)-1,3,4-oxadiazole(tBuPBD) and other compounds described in C. H. Chen et al., Macromol.Symp. 125, 1 (1997) and J. V. Grazulevicius, P. Strohriegl,“Charge-Transporting Polymers and Molecular Glasses”, Handbook ofAdvanced Electronic and Photonic Materials and Devices, H. S. Nalwa(ed.), 10, 233 (2001), both of which are incorporated herein byreference.

[0192] The present invention contemplates light emitting OEL displaysand devices which comprise an electroactive polymeric arylene. In oneembodiment, OEL displays can be made that emit light and that haveadjacent devices or elements that can emit light having different color.For example, FIG. 3 shows an OEL display 300 that includes a pluralityof OEL elements 310 adjacent to each other and disposed on a substrate320. Two or more adjacent elements 310 can be made to emit differentcolors of light, for example red, green, and blue. One or more ofelements 310 include an electroactive polymeric arylene.

[0193] The separation shown between elements 310 is for illustrativepurposes only. Adjacent devices may be separated, in contact,overlapping, etc., or different combinations of these in more than onedirection on the display substrate. For example, a pattern of parallelstriped transparent conductive anodes can be formed on the substratefollowed by a striped pattern of a hole transport material and a stripedrepeating pattern of red, green, and blue light emitting LEP layers,followed by a striped pattern of cathodes, the cathode stripes orientedperpendicular to the anode stripes. Such a construction may be suitablefor forming passive matrix displays. In other embodiments, transparentconductive anode pads can be provided in a two-dimensional pattern onthe substrate and associated with addressing electronics such as one ormore transistors, capacitors, etc., such as are suitable for makingactive matrix displays. Other layers, including the light emittinglayer(s) can then be coated or deposited as a single layer or can bepatterned (e.g., parallel stripes, two-dimensional pattern commensuratewith the anodes, etc.) over the anodes or electronic devices. Any othersuitable construction is also contemplated by the present invention.

[0194] In one embodiment, display 300 can be a multiple color display.In exemplary embodiments, each of the elements 310 emits light. Thereare many displays and devices constructions covered by the generalconstruction illustrated in FIG. 3. Some of those constructions arediscussed as follows.

[0195] OEL backlights can include emissive layers. Constructions caninclude bare or circuitized substrates, anodes, cathodes, hole transportlayers, electron transport layers, hole injection layers, electroninjection layers, emissive layers, color changing layers, and otherlayers and materials suitable in OEL devices. Constructions can alsoinclude polarizers, diffusers, light guides, lenses, light controlfilms, brightness enhancement films, and the like. Applications includewhite or single color large area single pixel lamps, for example wherean emissive material is provided by thermal stamp transfer, laminationtransfer, resistive head thermal printing, or the like; white or singlecolor large area single electrode pair lamps that have a large number ofclosely spaced emissive layers patterned by laser induced thermaltransfer; and tunable color multiple electrode large area lamps.

[0196] Low resolution OEL displays can include emissive layers.Constructions can include bare or circuitized substrates, anodes,cathodes, hole transport layers, electron transport layers, holeinjection layers, electron injection layers, emissive layers, colorchanging layers, and other layers and materials suitable in OEL devices.Constructions can also include polarizers, diffusers, light guides,lenses, light control films, brightness enhancement films, and the like.Applications include graphic indicator lamps (e.g., icons); segmentedalphanumeric displays (e.g., appliance time indicators); smallmonochrome passive or active matrix displays; small monochrome passiveor active matrix displays plus graphic indicator lamps as part of anintegrated display (e.g., cell phone displays); large area pixel displaytiles (e.g., a plurality of modules, or tiles, each having a relativelysmall number of pixels), such as may be suitable for outdoor displayused; and security display applications.

[0197] High resolution OEL displays can include emissive layers.Constructions can include bare or circuitized substrates, anodes,cathodes, hole transport layers, electron transport layers, holeinjection layers, electron injection layers, emissive layers, colorchanging layers, and other layers and materials suitable in OEL devices.Constructions can also include polarizers, diffusers, light guides,lenses, light control films, brightness enhancement films, and the like.Applications include active or passive matrix multicolor or full colordisplays; active or passive matrix multicolor or full color displaysplus segmented or graphic indicator lamps (e.g., laser induced transferof high resolution devices plus thermal hot stamp of icons on the samesubstrate); and security display applications.

[0198] One particularly useful embodiment for this type of thermallypatterned construction comprises the high resolution transfer of red,green and blue emitting emissive layers onto a common substrate using anelectroluminescent composition of the invention. High resolutiontransfer means that the rms (root mean square) edge roughness of thetransferred material is 5 micrometers or less.

[0199] Methods for Fabricating OEL Layers

[0200] Light emitting layers based on LEP materials or molecularly dopedpolymer films comprising electroactive arylene polymers of thisinvention may be fabricated by solution coating a thin layer of thematerial. Such thin layer methods are described, for example, in U.S.Pat. No. 5,408,109,incorporated herein by reference.

[0201] In certain applications, it is desirable to pattern one or morelayers of an organic electronic device onto a substrate, for example, tofabricate emissive displays. Methods for patterning include selectivetransfer, for example laser thermal transfer, photolithographicpatterning, inkjet printing, screen printing, and the like.

[0202] In one aspect, the present invention provides methods andmaterials for making an organic electronic device comprising selectivelytransfering an electroactive composition from a donor sheet to areceptor substrate; wherein the electroactive composition includes anelectroactive polymeric arylene. In one embodiment the present inventionprovides a donor sheet, comprising a transfer layer comprising theelectroactive composition which includes the electroactive polymericarylene.

[0203] A particularly useful method of forming organic electronicdevices of the present invention, for example, organicelectroluminescent devices, includes the transfer of one or moretransfer layers by laser thermal patterning. This method is describedin, for example, U.S. Pat. Nos. 6,358,664; 6,284,425; 6,242,152;6,228,555; 6,228,543; 6,221,553; 6,221,543; 6,214,520; 6,194,119;6,114,088; 5,998,085; 5,725,989; 5,710,097; 5,695,907; and 5,693,446,and in co-assigned U.S. patent application Ser. Nos. 09/853,062;09/844,695; 09/844,100; 09/662,980; 09/451,984; 09/931,598; and10/004,706, all of which are incorporated herein by reference. Theeffectiveness of the patterning process can depend upon the physicalproperties of the transfer layer.

[0204] One parameter is the cohesive, or film strength, of the transferlayer. During imaging, the transfer layer preferably breaks cleanlyalong the line dividing imaged and unimaged regions to form the edge ofa pattern. Highly conjugated polymers which exist in extended chainconformations, such as polyphenylenevinylenes, can have high tensilestrengths and elastic moduli comparable to that of polyaramide fibers.In practice, clean edge formation during the laser thermal imaging oflight emitting polymers can be challenging. The undesired consequence ofpoor edge formation is rough, torn, or ragged edges on the transferredpattern. Another parameter is the strength of the bond formed betweenthe transfer layer and the receptor surface. This strength may beinfluenced by the solubility parameter compatability of the transferlayer and the receptor surface.

[0205] In some instances, it is desirable to select the material on thesubstrate surface and the material to be transferred (e.g., theelectroactive polymeric arylene material or a blend comprising suchpolymer) such that the solubility parameters are compatible to improveor even make possible thermal transfer or other patterning methods. Asan example, the materials can be selected such that the difference inthese solubility parameters is no more than 4 J^(1/2) cm^(−3/2) and,preferably, no more than 2 J^(1/2) cm^(−3/2) as determined according to“Properties of Polymers; Their Correlation with Chemical Structure;their Numerical Estimation and Prediction from Additive GroupContributions.” third, completely revised edition by D. W. Van Krevelen;Elsevier Science Publishers B.V., 1990; Chapter 7, pp 189-225,incorporated herein by reference.

[0206] The solubility parameter of a polymer can be determined frommeasurements of the extent of equilibrium swelling of the polymer in arange of solvents of differing solubility parameters. The solubilityparameters of the solvents themselves can be determined from their heatsof evaporation. The solubility parameter δ is related to the cohesiveenergy E_(coh) and the specific volume V by the relationshipδ=(E_(coh)/V)^(1/2). For solvents of low molecular weight, the cohesiveenergy is closely related to the molar heat of evaporation ΔH_(vap)according to E_(coh). =ΔH_(vap)−pΔV=ΔH_(vap)−RT. Thus, E_(coh) and δ canbe calculated from the heat of evaporation of the solvent or from thecourse of the vapor pressure as a function of temperature.

[0207] Because polymers cannot be evaporated, indirect methods have tobe used for determination of their solubility parameter. To determinethe solubility parameter of the polymer, the equilibrium swelling of thepolymer in a variety of solvents of differing δ is measured and a plotof equilibrium swelling of the polymer vs. the solubility parameter ofthe solvents is generated. The solubility parameter of the polymer isdefined as the point on this plot where maximum swelling is obtained.Swelling will be less for solvents having solubility parameters that areless than or greater than that of the polymer. There are several methodsfor theoretically estimating the solubility parameter of a polymer basedon the additive contributions of functional groups present in thepolymer as outlined in the above-cited reference.

[0208] Organic electronic devices containing an electroactivecomposition comprising the electroactive polymeric arylene of thepresent invention and optionally other materials for light emission canbe made at least in part by selective thermal transfer of thecomposition from a thermal transfer donor sheet to a desired receptorsubstrate. For example, light emitting polymer displays and lamps can bemade by coating an LEP layer on a donor sheet and then selectivelytransferring the LEP layer alone or along with other device layers ormaterials to the display (receptor) substrate.

[0209]FIG. 2 shows an example of a thermal transfer donor sheet 200suitable for use in the present invention. Donor element 200 includes abase substrate 210, an optional underlayer 212, an optionallight-to-heat conversion layer (LTHC layer) 214, an optional interlayer216, and a transfer layer 218 comprising an electroactive polymericarylene of the present invention. Other layers can also be present.Examples of suitable donors or layers of donors are disclosed in U.S.Pat. Nos. 6,358,664; 6,284,425; 6,242,152; 6,228,555; 6,228,543;6,221,553; 6,221,543; 6,214,520; 6,194,119; 6,114,088; 5,998,085;5,725,989; 5,710,097; 5,695,907; and 5,693,446, and in co-assigned U.S.patent application Ser. Nos. 09/853,062; 09/844,695; 09/844,100;09/662,980; 09/451,984; 09/931,598; and 10/004,706, all of which areincorporated herein by reference.

[0210] Emissive organic materials, including LEPs or molecularly dopedpolymer films comprising electroactive polymeric arylenes of thisinvention, can be transferred or selectively transferred in the transferlayer from a donor sheet to a receptor substrate by placing the transferlayer of the donor element adjacent to the receptor and selectivelyheating the donor element. Methods for the transfer or the selectivetransfer are described in, for example, U.S. Pat. No. 6,242,152.Transfer layers can also be transferred from donor sheets withoutselectively transferring the transfer layer. For example, a transferlayer can be formed on a donor substrate that, in essence, acts as atemporary liner that can be released after the transfer layer iscontacted to a receptor substrate, typically with the application ofheat or pressure. Such a method, referred to as lamination transfer, canbe used to transfer the entire transfer layer, or a large portionthereof, to the receptor.

[0211] Materials from separate donor sheets can be transferred adjacentto other materials on a receptor to form adjacent devices, portions ofadjacent devices, or different portions of the same device.Alternatively, materials from separate donor sheets can be transferreddirectly on top of, or in partial overlying registration with, otherlayers or materials previously patterned onto the receptor by thermaltransfer or some other method (e.g., photolithography, depositionthrough a shadow mask, etc.). A variety of other combinations of two ormore donor sheets can be used to form a device, each donor sheet formingone or more portions of the device. It will be understood that otherportions of these devices, or other devices on the receptor, may beformed in whole or in part by any suitable process includingphotolithographic processes, ink jet processes, and various otherprinting or mask-based processes, whether conventionally used or newlydeveloped.

[0212] In FIG. 2 the donor substrate 210 can be a polymer film. Suitablefilms are described in U.S. Pat. Nos. 6,242,152 and 6,228,555.

[0213] In FIG. 2 optional underlayer 212 may be coated or otherwisedisposed between a donor substrate and the LTHC layer, for example tocontrol heat flow between the substrate and the LTHC layer duringimaging or to provide mechanical stability to the donor element forstorage, handling, donor processing, or imaging. Examples of suitableunderlayers and methods of providing underlayers are disclosed in U.S.Pat. No. 6,228,555 and in co-assigned U.S. patent application Ser No.09/743,114, incorporated herein by reference.

[0214] The underlayer can include materials that impart desiredmechanical or thermal properties to the donor element. For example, theunderlayer can include materials that exhibit a low specific heat xdensity or low thermal conductivity relative to the donor substrate.Such an underlayer may be used to increase heat flow to the transferlayer, for example to improve the imaging sensitivity of the donor.

[0215] The underlayer may also include materials for their mechanicalproperties or for adhesion between the substrate and the LTHC. Using anunderlayer that improves adhesion between the substrate and the LTHClayer may result in less distortion in the transferred image. As anexample, in some cases an underlayer can be used that reduces oreliminates delamination or separation of the LTHC layer, for example,that might otherwise occur during imaging of the donor media. This canreduce the amount of physical distortion exhibited by transferredportions of the transfer layer. In other cases, however it may bedesirable to employ underlayers that promote at least some degree ofseparation between or among layers during imaging, for example toproduce an air gap between layers during imaging that can provide athermal insulating function. Separation during imaging may also providea channel for the release of gases that may be generated by heating ofthe LTHC layer during imaging. Providing such a channel may lead tofewer imaging defects.

[0216] The underlayer may be substantially transparent at the imagingwavelength, or may also be at least partially absorptive or reflectiveof imaging radiation. Attenuation or reflection of imaging radiation bythe underlayer may be used to control heat generation during imaging.

[0217] In FIG. 2, an LTHC layer 214 can be included in donor sheets ofthe present invention to couple irradiation energy into the donor sheet.The LTHC layer preferably includes a radiation absorber that absorbsincident radiation (e.g., laser light) and converts at least a portionof the incident radiation into heat to enable transfer of the transferlayer from the donor sheet to the receptor. Suitable LTHC layers aredescribed in, for example, U.S. Pat. Nos. 6,242,152, and 6,228,555.

[0218] In FIG. 2, an optional interlayer 216 may be disposed between theLTHC layer 214 and transfer layer 218. The interlayer can be used, forexample, to minimize damage and contamination of the transferred portionof the transfer layer and may also reduce distortion in the transferredportion of the transfer layer. The interlayer may also influence theadhesion of the transfer layer to the rest of the donor sheet.Typically, the interlayer has high thermal resistance. Preferably, theinterlayer does not distort or chemically decompose under the imagingconditions, particularly to an extent that renders the transferred imagenon-functional. The interlayer typically remains in contact with theLTHC layer during the transfer process and is not substantiallytransferred with the transfer layer.

[0219] Suitable interlayers are described in, for example, U.S. Pat.Nos. 6,242,152, and 6,228,555.

[0220] In FIG. 2, a thermal transfer layer 218 is included in donorsheet 200. Transfer layer 218 includes an electroactive polymericarylene of the present invention and can include any other suitablematerial or materials, disposed in one or more layers, alone or incombination with other materials. Transfer layer 218 is capable of beingselectively transferred as a unit or in portions by any suitabletransfer mechanism when the donor element is exposed to direct heatingor to imaging radiation that can be absorbed by light-to-heat convertermaterial and converted into heat.

[0221] The present invention further provides a light emitting transferlayer that comprises an electroactive polymeric arylene of FormulasV-VIII. One way of providing the transfer layer is by solution coatingthe light emitting material onto the donor substrate or any of thelayers described supra, i.e., underlayer, interlayer, light-to-heatconverting layer. In this method, the light emitting material can besolubilized by addition of a suitable compatible solvent, and coatedonto the donor substrate or any one of the above layers by spin-coating,gravure coating, Mayer rod coating, knife coating and the like. Thesolvent chosen preferably does not undesirably interact with (e.g.,swell or dissolve) any of the already existing layers in the donorsheet. The coating can then be annealed and the solvent evaporated toleave a transfer layer.

[0222] The transfer layer can then be selectively thermally transferredfrom the resulting donor sheet or element to a proximately locatedreceptor substrate. There can be, if desired, more than one transferlayer so that a multilayer construction is transferred using a singledonor sheet. Suitable receptor substrates are described, for example, inU.S. Pat. Nos. 6,242,152 and 6,228,555.

[0223] Receptor substrates can be pre-patterned with any one or more ofelectrodes, transistors, capacitors, insulator ribs, spacers, colorfilters, black matrix, hole transport layers, electron transport layers,and other elements useful for electronic displays or other devices.

[0224] The invention is further described by the following examples,which are provided for illustration only and are not intended to belimiting in any way.

EXAMPLES

[0225] All reagents were obtained from Aldrich Chemical Company,Milwaukee, Wis. unless otherwise stated. All compounds made werecharacterized by NMR spectroscopy.

[0226] Glossary

[0227] 1,4-Benzenediboronic acid bis(neopentyl glycol) cyclic ester wasobtained from Lancaster Synthesis Ltd., Windam, N.H.

[0228]N,N′-Bis(4-bromophenyl)-N,N′-bis(4-butylphenyl)benzene-1,4-diamine wasobtained from American Dye Source, Baie D'Urfe, Quebec, Canada.

[0229] 2,5-Bis(hexyl)-1,4-benzenebis(boronic acid) was obtained fromFrontier Scientific Inc., Logan, Utah.

[0230]2,7-Bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9,9-dioctylfluorenecan be made as described in Ranger et al., Chem. Commun. 1597-1598(1997), incorporated herein by reference.

[0231] 4-Bromo-N,N-diphenylaniline can be made as described in Creasonet al., J. Org. Chem. 37, 4440-4446 (1972), incorporated herein byreference.

[0232] (bthpy)₂Ir(acac)—can be made as described in Lamansky et al., J.Am. chem. Soc. 123(18), 4304-4312 (2001), incorporated herein byreference.

[0233] CBP—a hole transporting agent, 4,4′-bis(carbazol-9-yl)biphenyl,available from H. W. Sands, Jupiter, Fla.

[0234] 4,7-Dibromo-2,1,3-benzothiadiazole can be made as described inPilgram et al., J. Heterocycl. Chem., 7, 629-633 (1970), incorporatedherein by reference.

[0235] 3,6-Dibromo-9-phenylcarbazole can be made as described in Park etal., Tetrahedron, 42, 12707-12714 (1998), incorporated herein byreference.

[0236] 3,9-Dibromo-perylene and 3,10-dibromo-perylene can be made asdescribed in Zinke et al., Chem. Ber. 74, 107-112 (1941), incorporatedherein by reference.

[0237] 2,7-Dibromo-9,9-dioctyl-fluorene can be made as described inRanger et al., Can. J. Chem., 1571-1577(1998), incorporated herein byreference.

[0238] HT—a low molecular weight (Mw<1000), phenyl capped, holetransporting polymer, comprising poly(9-phenylcarbazol-3,6-diyl), whichcan be prepared by bis(1,5-cyclooctadiene)nickel (0) mediatedpolymerization of 3,6-dibromo-9-phenylcarbazole as described in Example3 of Euopean Patent No. 1011154, incorporated herein by reference, forthe polymerization of fluorene monomers.

[0239] Ir(ppy)3—a molecular emitter, tris(2-phenylpyridine) iridium(III), available from H. W. Sands, Jupiter, Fla.

[0240] NPB—N,N′-di(naphthalen-2-yl)-N,N′-diphenylbenzidine, availablefrom H. W. Sands, Jupiter, Fla.

[0241] PBD—An electron transport agent,2-(4-biphenyl)-5-(4-t-butylphenyl)-1,3,4-oxadiazole, available from H.W. Sands, Jupiter, Fla.

[0242] PEDT/PSS—copolymer (poly(3,4-ethylenedioxythiophene)/polystyrenesulfonate, available as Baytron™ P4083 from Bayer A G, Leverkusen,Germany.

[0243] PhO(CH₂)₂O(CH₂)₂I can be made as described in Otera et al., Bull.Chem. Soc. Jpn. 2964-2967 (1981), incorporated herein by reference.

[0244] PS-DPAS—a hole transporting polymer,polystyrene-diphenylaminostyrene copolymer prepared as follows.

[0245] p-Diphenylaminostyrene monomer was synthesized by a preparationsimilar to that described by Tew et al., Angew. Chem. Int. Ed.39,517(2000). To a mixture of 4-(diphenylamino)benzaldehyde (20.06 g, 73mmol, Fluka Chemicals, Milwaukee, Wis.), methyltriphenyl phosphoniumbromide (26.22 g, 73 mmol) and dry tetrahydrofuran (450 mL) undernitrogen was added a 1M solution of potassium t-butoxide intetrahydrofuran (80 mL, 80 mmol) over 5 minutes. The mixture was stirredfor 17 hours at room temperature. Water (400 mL) was added and thetetrahydrofuran was removed under reduced pressure. The mixture wasextracted with ether, and the combined organic layers were dried overMgSO₄ and concentrated under vacuum. The crude solid was purified bycolumn chromatography on silica gel using a 50/50 mixture of methylenechloride and hexane to give a yellow solid that was furtherrecrystallized once from hexane (15.37 g, 78%). 1H NMR (400 MHz, CDCl₃)(7.21-7.32 (m, 6H), 7.09 (d, J=7.6 Hz, 4H), 7.02 (m, 4H), 6.66 (dd,J=17.6 Hz, 11.0 Hz, 1H), 5.63 (dd, J=17.6, 1H), 5.15 (dd, J=11.0 Hz,1H); 13C NMR (100 MHz, CDCl3) ( 147.5, 136.1, 131.8, 129.1, 126.9,124.3, 123.5, 122.8, 112.0.

[0246] To synthesize the polymer, a round bottom glass reactor was bakedout under vacuum at 200° C. for 2 hours, then allowed to cool. Thereactor was filled with dry nitrogen. Subsequently, 71.8 g ofcyclohexane and 4.4 mL of tetrahydrofuran (THF) were added to thereactor by syringe. The THF was distilled from sodium/benzophenone undernitrogen prior to use, in order to scavenge water and oxygen. Thecyclohexane was dried by passage through activated basic alumina,followed by sparging with nitrogen gas for 30 minutes prior to use.After addition of the solvents, the reaction flask was cooled to 3° C.in an ice water bath, after which 0.02 mL of styrene was added to thereactor. The styrene had previously been passed through activated basicalumina to remove inhibitors and water, and sparged with nitrogen gas toremove oxygen. A solution of s-butyllithium in cyclohexane (0.4 mL, 1.3mol/L) was subsequently added to the reactor. The solution immediatelyturned orange, characteristic of the formation of polystyryl anion. Anadditional 1.78 mL of styrene was subsequently added to the reactor.After stirring at 3° C. for 2 hours, a solution ofp-diphenylaminostyrene (1.61 g) in cyclohexane (20 mL) was added to thereactor by cannula. This solution had previously been degassed byrepeatedly freezing it with liquid nitrogen and exposing it to vacuum.The solution was stirred overnight while warming to room temperature.The reaction was then terminated by addition of methanol, precipitatedinto a mixture of methanol and isopropanol, and dried under in a vacuumoven overnight, yielding 3.2 g of polymer. The resulting PS-DPAS blockpolymer contained 74.1 mol % styrene and 25.9 mol %p-diphenylaminostyrene, based on ¹³C NMR. The molecular weight of theblock copolymer was 7700 g/mol, based on gel permeation chromatographyin THF against polystyrene standards.

[0247] Pt(OEP)—a molecular emitter, platinum (II) octaethyl porphyrin,available from H. W. Sands, Jupiter, Fla.

[0248] PVK—a hole transporting agent, poly(9-vinylcarbazole, availablefrom Aldrich, Milwaukee, Wis.

[0249] Tetrakis(triphenylphosphine) palladium (0) was obtained fromStrem Chemical, Newburyport, Mass.

[0250] 4,4,5,5-Tetramethyl-2-phenyl-1,3,2-dioxaborolane can be made frombromobenzene following the general procedure of borolanation as reportedin Ranger et al., Chem. Commun. 1597-1598 (1997), incorporated herein byreference.

[0251] TMC—a molecular emitter, 3-thienyl-7-methoxycoumarin can beprepared by methods outlined in Sreenivasulu, B.; Sundaramurthy, V.;Subba Rao, N. V. Proceedings of the Indan Academy of Sciences, Sect A,78, 159-168 (1973), incorporated herein by reference.

[0252] TPD—A hole transporting agent,N,N′-bis(3-methylphenyl)-N,N′-bis(phenyl)benzidine, available from H. W.Sands, Jupiter, Fla.

[0253] Monomers

Example 1

[0254] Synthesis of2-(2,5-Dichlorophenyl)-5-[4-(octyloxy)phenyl]-1,3,4-oxadiazole (2)

[0255] Part A

[0256] Synthesis of Methyl 4-octoxybenzoate

[0257] Into a flask was introduced 251.0 g (1.65 mol) of methyl4-hydroxybenzoate, 276.37 g (1.99 mol) potassium carbonate and 1200 g ofacetone. This was refluxed for 45 min followed by the dropwise additionof 386.17 g (1.99 mol ) of 1-octylbromide over a 1 hour period. Thereaction mixture was refluxed for two days. Filtration of the cooledreaction mixture and evaporation of the filtrate gave an oil. This wastaken up in ethyl acetate and extracted with 5% NaOH (2×100 ml) followedby water (2 100 ml). The organic layer was dried (MgSO₄), concentrated,and transferred to a 1L three necked flask. The contents of the flaskwas subjected to high vacuum distillation to remove the excess1-octylbromide. The pot residue was essentially pure methyl4-octoxybenzoate (376 g, 86%).

[0258] Part B

[0259] Synthesis of 4-Octoxybenzoyl Hydrazide

[0260] To the contents of the flask from Part A was added 387.14 g of98% hydrazine. This was refluxed for 5 hours (106° C.). The cooledsolution was poured into 3L of water and the precipitated solidfiltered, washed with copious amounts of water and dried in vacuo togive 4-octylbenzoyl hydrazide (343 g, 91% yield, mp 90° C.).

[0261] Part C

[0262] Synthesis of 2,4-Dichlorobenzoyl Chloride

[0263] Into a 2 L flask fitted with a reflux condenser and magneticstir-bar was introduced 150 g (0.785 mol) 2,5-dichlorobenzoic acid and575 ml (7.85 mol) of thionyl chloride. The mixture was refluxed for 8hours. Most of the thionyl chloride was distilled off followed byremoval of the remainder by rotary evaporation. Distillation gave 130 g(79% yield) of 2,4-dichlorobenzoyl chloride (pot temperature 110° C.;distillation temp 70° C./0.70 mm Hg).

[0264] Part D

[0265] Synthesis of 2,5-Dichloro-N′-[4-(octyloxy)benzoyl]benzohydrazide

[0266] Under a blanket of nitrogen, 8.8 g (0.087 mol)2,4-dichlorobenzoyl chloride was added to a solution of 23.0 g (0.087mol) 4-octoxybenzoyl hydrazine and 12.13 ml (8.8 g, 0.087 mol) freshlydistilled triethylamine in 348 ml dry chloroform. After about one hourof stirring a dense white precipitate of the required product wasformed. Stirring was continued until the next day. The product wascollected by filtration and recrystallized from ethanol/water to give 31g (81.5% yield) of 2,5-dichloro-N′-[4-(octyloxy)benzoyl]benzohydrazideas a white solid.

[0267] Part E

[0268] Synthesis of2-(2,5-Dichlorophenyl)-5-[4-(octyloxy)phenyl]-1,3,4-oxadiazole (2)

[0269] Into a 250 ml flask fitted with a mechanical stirrer andthermometer was introduced 30 g (0.0686 mol)2,5-dichloro-N′-[4-(octyloxy)benzoyl]benzohydrazide and 181 mlphosphorus oxychloride. This was refluxed and stirred for 8 hrs. About100 ml of phosphorus oxychloride was distilled off under reducedpressure. The cooled residue was poured onto water and crushed ice withmanual stirring and allowed to stand until the ice had melted. Theprecipitated white solid was collected by filtration, dried andrecrystallized from ethanol. There was obtained 25.7 g (89% yield, mp86° C.) of2-(2,5-dichlorophenyl)-5-[4-(octyloxy)phenyl]-1,3,4-oxadiazole (2). Thestructure was confirmed unambiguously by 1D and 2D NMR techniques andgave the following: ¹H-NMR (500 MHz, CDCl₃) 0.89 (3H, t), 1.31 (8H, m),1.46 (2H, q), 1.79 (2H, q), 6.97 (2H, d), 7.38 (1H, dd), 7.44 (1H, d),8.01 (2H, d), 8.06 (1H, d); ¹³C-NMR (500 MHz, CDCl₃) 13.90 (C-28),22.44, 25.79, 28.91, 29.01, 29.13, 31.59, 68.08 (C-21), 114.78 (C14 andC-16), 115.37 (C-12), 124.27 (C-6), 128.58 (C-13 and C-17), 130.23(C-11), 130.87 (C-7), 131.75, 132.20, 132.87 (C-10), 161.03, 161.98(C-15), 164.95 (C-5).

Example 2

[0270] Synthesis of2-(4-tert-butylphenyl)-5-(2,5-dichlorophenyl)-1,3,4-oxadiazole (3)

[0271] Part A

[0272] Synthesis of N-(4-tert-Butylbenzoyl)-2,5-dichlorobenzohydrazide

[0273] 4-tert-Butylbenzoyl hydrazide (185 g, 0.96 mol) and triethylamine(97.37 g, 0.96 mol) freshly distilled from calcium hydride were added to4L of dichloromethane in a 10L flask. To this was added with mechanicalstirring 201.5 g of 2,4-dichlorobenzoyl chloride. No precipitation ofthe product was observed after three hours and the reaction was allowedto stir at room temperature until the next day. The product wasprecipitated by the addition of 4L hexane. Filtration, hexane washingand drying at 80° C. in a forced air oven gave the product in 99% yield.

[0274] Part B

[0275] Synthesis of2-(4-tert-butylphenyl)-5-(2,5-dichlorophenyl)-1,3,4-oxadiazole (3)

[0276] Into a 2L flask was introduced 200 gN-(4-tert-butylbenzoyl)-2,5-dichlorobenzohydrazide (0.55 mol) and 1378ml phosphorus oxychloride (2267 g, 14.78 mol). This was refluxed for 8hrs and the solvent then evaporated under slight vacuum. The residue waspoured onto crushed ice and allowed to stand until the next day.Filtration gave a sticky mass, which was dissolved in methanol, andsolid material was obtained by addition of a little water. Filtrationand drying gave 112 g of the required product as a white crystallinesolid (59% yield).

Example 3

[0277] Synthesis of2-(2,5-Dibromophenyl)-5-[4-(octyloxy)phenyl]1,3,4-oxadiazole (1)

[0278] Part A

[0279] Synthesis of 2,5-Dibromobenzoyl Chloride

[0280] By the general method of Part C of Example 1, the reaction of50.0 g (0.1786 mol) 2,5-dibromobenzoic acid with 150 mL thionyl chloridegave after distillation 40 g of 2,5-dibromobenzoyl chloride.

[0281] Part B

[0282] Synthesis of 2,5-Dibromo-N′-[4-(octyloxy)benzoyl]benzohydrazide

[0283] By the general method of Part A, Example 2, 2,5-dibromobenzoylchloride (57.43 g, 0.11925 mol), 4-octoxybenzoyl hydrazide (50.88 g,0.1925 mol), and triethylamine (27 ml, 19.48 g, 0.1925 mol) were reactedin 800 ml methylene chloride to give a product. Re-crystallization ofthe product from DMF/water gave 79.38 g (78% yield)2,5-dibromo-N′-[4-(octyloxy)benzoyl]benzohydrazide.

[0284] Part C

[0285] Synthesis of2-(2,5-Dibromophenyl)-5-[4-(octyloxy)phenyl]1,3,4-oxadiazole (1)

[0286] By the general method of Part B of Example 2, cyclocondensationof 39.1 g (0.0743 mol) ofN-(2,5-dibromobenzoyl)-4-(octyloxy)benzohydrazide with 203 ml phosphorusoxychloride for 8 hrs gave, after recrystallizing from EtOH/water, 33.6g (89% yield)2-(2,5-dibromophenyl)-5-[4-(octyloxy)phenyl]1,3,4-oxadiazole (1).

Example 4

[0287] Synthesis of2-(2,5-Dichlorophenyl)-5-(pentafluorophenyl)-1,3,4-oxadiazole (10)

[0288] Part A

[0289] Synthesis of 2,5-Dichlorobenzohydrazide

[0290] Into a flask was introduced 30 g (0.1463 mol) methyl2,5-dichlorobenzoate and 46.89 g (1.463 mol) hydrazine. This wasrefluxed for 5 hours. The cooled reaction mixture was poured into anexcess of water, to precipitate an off-white solid. Filtration anddrying under vacuum gave 30 g solid. A ¹H-NMR showed that the materialwas fairly pure 2,5-dichlorobenzohydrazide and was therefore usedwithout further purification.

[0291] Part B

[0292] Synthesis of 2,5-Dichloro-N′-(pentafluorobenzoyl)benzohydrazide

[0293] By the general method of Part A of Example 2, 21.0 g (0.1024 mol)2,5-dichlorobenzohydrazide with 23.6 g (0.1024 mol) pentafluorobenzoylchloride and 14.3 ml (0.1026 mol) triethylamine in methylenechloride/DMF (1L, 1:1) gave, after re-crystallizing from DMF/water,22.51 g (55% yield, mp 227-232° C.)2,5-dichloro-N′-(pentafluorobenzoyl)benzohydrazide.

[0294] Part C

[0295] Synthesis of2-(2,5-Dichlorophenyl)-5-(pentafluorophenyl)-1,3,4-oxadiazole (10)

[0296] By the general method of Part B of Example 2, the reaction of21.0 g (0.05377 mol) 2,5-dichloro-N′-(pentafluorobenzoyl)benzohydrazidein POCl₃ gave a product which was recrystallized from ethanol/water togive 16.59 g (81% yield) of2-(2,5-dichlorophenyl)-5-(pentafluorophenyl)-1,3,4-oxadiazole (10).

Example 5

[0297] Synthesis of2-(2,5-Dichlorophenyl)-5-(9,9-dioctyl-9H-fluoren-2-yl)-1,3,4-oxadiazole(13)

[0298] Part A

[0299] Synthesis of 2-Bromo-9,9-dioctylfluorene

[0300] A 3L flask fitted with a mechanical stirrer was charged with2-bromofluorene (45 g, 183.6 mmole) and 150 mL DMSO. Under a N₂atmosphere was added 80 mL of a 50% aqueous NaOH solution and 2.72 g ofbenzyltriethylammonium chloride (2.72 g, 11.98 mmole). This was stirredfor 2 h at RT. With vigorous mechanical stirring, n-octylbromide (84.96g, 440 mmole) was added via a dropping funnel (exotherm). Stirring wascontinued for 2 hours. To the reaction mixture was added 500 mL of a 1:1mixture of water/ether, and the organic layer separated and was washedsuccessively with brine and then water. Drying over magnesium sulfateand evaporation of the solvent gave an oil. Purification by columnchromatography (silica gel; hexane as the mobile phase) gave 67 g (78%yield) of 2-bromo-9,9-dioctylfluorene as a pale oil.

[0301] Part B

[0302] Synthesis of 9,9-Dioctyl-9H-fluorene-2-carboxylic Acid

[0303] Into a flask fitted with a nitrogen inlet and rubber septum wereintroduced 2-bromo,-9,9-dioctylfluorene (34.18 g, 72.8 mmole) and drytetrahydrofuran (300 mL). The solution was cooled to -60° C. and n-butyllithium (29.1 mL, 2.5M in hexanes, 72.8 mmole) added via a syringe. Thereaction mixture was observed to turn red. After stirring for 1 hour at−60° C., the reaction mixture was poured onto powdered dry-ice and leftto stand overnight. The mixture was acidified with 1M HCl and extractedwith chloroform. The chloroform extract was washed with water, driedover magnesium sulfate and concentrated to give the required acid as anoil.

[0304] Part C

[0305] Synthesis of 9,9-Dioctyl-9H-fluorene-2-carbonyl Chloride

[0306] 9,9-Dioctyl-9H-fluorene-2-carboxylic acid (32.36 g, 74.5 mmole)was refluxed in thionyl chloride (93 g, 782 mmole) for 8 hrs. Unreactedthionyl chloride was distilled off and the residue material used withoutfurther purification.

[0307] Part D

[0308] Synthesis of2,5-Dichloro-N′-[(9,9-dioctyl-9H-fluoren-2-yl)carbonyl]benzohydrazide

[0309] 2,5-Dichlorobenzohydrazide (one equivalent) and triethylamine(one equivalent) were warmed in 500 mL of 1,2-dichloroethane until thesolid material had dissolved. On cooling,9,9-dioctyl-9H-fluorene-2-carbonyl chloride (one equivalent) was addedand the mixture stirred at RT for two days. The insolubles were filteredoff and the filtrate evaporated to give an oil. This was taken up inheptane and the precipitated solid filtered off. The remaining solutionwas dried (MgSO₄) and concentrated to give the desired intermediate.

[0310] Part E

[0311] Synthesis of2-(2,5-Dichlorophenyl)-5-(9,9-dioctyl-9H-fluoren-2-yl)-1,3,4-oxadiazole(13)

[0312]2,5-Dichloro-N′-[(9,9-dioctyl-9H-fluoren-2-yl)carbonyl]benzohydrazide(20.0 g, 32.17 mmole) and phosphorus oxychloride (91 mL) were refluxedfor 8 hrs. The reaction was distilled until about half the volumeremained. The pot fraction was cooled and poured onto an ice/watermixture with constant stirring. The sticky paste that formed wasextracted into hexane and the hexane extract dried and concentrated.Column chromatography (5% ethyl acetate in hexane) gave 14.98 g (77%yield) of the desired compound as an oil.

Example 6

[0313] Synthesis of2-(3,5-Dichlorophenyl)-5-[4-(octyloxy)phenyl]-1,3,4-oxadiazole (4)

[0314] By the general method for the synthesis of2-(2,5-dibromophenyl)-5-[4-(octyloxy)phenyl]-1,3,4-oxadiazole (1) inExample 3, the reaction of 3,5-dichlorobenzoyl chloride (20.0 g, 0.010mole) with 4-octoxybenzoyl hydrazide (25.24 g, 0.010 mole) gave theintermediate 3,5-dichloro-N′-[4-(octyloxy)benzoyl]benzohydrazide (25 g,60% yield). Cyclocondensation of the intermediate3,5-dichloro-N′-[4-(octyloxy)benzoyl]-benzohydrazide (16.0 g) with POCl₃(83 mL) gave the required2-(3,5-dichlorophenyl)-5-[4-(octyloxy)phenyl]-1,3,4-oxadiazole (4)(11.16 g, 73% yield).

Example 7

[0315] Synthesis of2-(3,5-Dibromophenyl)-5-[4-(octyloxy)phenyl]-1,3,4-oxadiazole (5)

[0316] By the general method for the synthesis of2-(2,5-dibromophenyl)-5-[4-(octyloxy)phenyl]-1,3,4-oxadiazole (1) inExample 3, the reaction of 3,5-dibromobenzoyl chloride (20.13 g, 0.06747mole) with 4-octoxybenzoyl hydrazide (17 g, 0.06747 mole) gave theintermediate 3,5-dibromo-N′-[4-(octyloxy)benzoyl]benzohydrazide (12.87g, 36% yield). Cyclocondensation of the intermediate3,5-dibromo-N′-[4-(octyloxy)benzoyl]-benzohydrazide (12.17 g) with POCl₃(63 mL) gave the required2-(3,5-dibromophenyl)-5-[4-(octyloxy)phenyl]-1,3,4-oxadiazole (5) (6.12g, 52% yield).

Example 8

[0317] Synthesis of3-(2,5-Dichlorophenyl)-4-(4-methoxyphenyl)-5-[4-(octyloxy)phenyl]-4H-1,2,4-triazole(8)

[0318] Into a 1L round-bottomed flask fitted with a mechanical stirrer,reflux condenser and nitrogen inlet were introduced2,5-dichloro-N′-[4-(octyloxy)benzoyl]benzohydrazide (40 g, 0.09146 mole,1 equivalent), p-anisidine (67.60 g, 0.5487 mole, 6 equivalents) and 300mL 1,2-dichlorobenzene. Mechanical stirring resulted in partialsolvation of the solids. Phosphorus trichloride (12.56 g, 0.0146 mole, 1equivalent) was added and the contents of the flask heated at 180° C.for 12 hrs. The solvent was distilled off under a light vacuum and theresidue transferred to a 2L flask with 1L of a 1:1 acetone/heptanemixture. The solid material was filtered off and dissolved in acetone.Enough heptane was added to precipitate a purple-colored oily sludge.Heptane dilution of a test sample of the acetone/heptane layer ensuredthat the oily sludge had been completely precipitated. Theacetone/heptane layer was decanted off and diluted further with a largeexcess of heptane to precipitate a white solid. This was filtered off,dissolved in acetone and re-precipitated with heptane. Filtration anddrying gave3-(2,5-dichlorophenyl)-4-(4-methoxyphenyl)-5-[4-(octyloxy)phenyl]-4H-1,2,4-triazole(8) (16.25 g, 34% yield).

Example 9

[0319] Synthesis of 2,7-Dibromo-9,9-bis(3,6-dioxaheptyl)-fluorene

[0320] Benzyltriethylammonium chloride (3.19 g, 14 mmole, 0.077 eq) and2,7-dibromofluorene (59 g, 182 mmole, 1 eq) were suspended in 178 mLDMSO. 50% aqeous NaOH (80 mL) was added.1-Bromo-2-(2-methoxyethoxy)ethane (80 g, 437 mmole, 2.4 eq) was thenadded in small portions. The reaction was stirred at room temperaturefor 2 hours before it was stopped and the aqueous layer was extractedwith ether. The combined ether layers were washed with water five timesand dried over Na₂SO₄. The organic layer was filtered, evaporated todryness, and the residual was flash chromatographed on a silica-gelcolumn to give 73 g of the pure compound in a yield of 86%.

Example 10

[0321] Synthesis of2,7-Dibromo-9,9-bis(3,6-dioxahexyl-6-phenyl)-fluorene

[0322] 2,7-Dibromo-9,9-bis(3,6-dioxahexyl-6-phenyl)-fluorene wassynthesized from PhO(CH₂)₂O(CH₂)₂I and 2,9-dibromofluorene following theprocedure essentially as described in Example 9.

[0323] End Capping Groups

Example 11

[0324] Synthesis ofN,N-diphenyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)aniline

[0325] n-Butyllithium was added dropwise via syringe to a −78° C.(acetone-dry ice cooling bath) solution of 4-bromo-N,N-diphenylaniline(24 g, 0.074 mole) in 175 ml dry THF. Stirring was continued at −78° C.for an hour and then at −50° C. for an hour. The mixture was cooled to−78° C. and 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (17.22g, 0.0925 mole) added via syringe in one portion. The temperature wasmaintained at −78° C. for three hours. The cooling bath was removed andthe reaction left to warm to room temperature while standing for 12hours. The reaction mixture was poured into saturated ammonium acetateand extracted with ether. The ether layer was dried over magnesiumsulfate and concentrated to give a viscous oil. Purification by columnchromatography (silica gel eluting with hexane:toluene mixtures ofincreasing gradient from 100% hexane to 40% hexane) gaveN,N-diphenyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)aniline asan oil (19.9 g, 72.8% yield), which slowly crystallized to a solid onstanding.

Example 12

[0326] Synthesis of4-[9,9-Dioctyl-7-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9H-fluoren-2-yl]-N,N-diphenylaniline

[0327] 4-Bromo-N,N-diphenylaniline (19.44 g, 60 mmole, 1 equiv),2-[9,9-dioctyl-7-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9H-fluoren-2-yl]-4,4,5,5-tetramethyl-1,3,2-dioxaborolane(76.9 g, 120 mmole, 2 equiv), Aliquat™ 336 (tricaprylylmethylammoniumchloride) (6 g, 15 mmole, 0.25 equiv) and 2M sodium carbonate solution(75 mL, 150 mmole, 2.5 equiv) were added to 600 mL of toluene. This waspurged with a stream of nitrogen for about 30 min. Under a nitrogenpurge, tetrakis(triphenylphosphine) palladium (0) (348 mg, 0.30 mmole,0.005 equiv) was added. The reaction mixture was then refluxed for 16hrs. The reaction was cooled to room temperature and water added. Theorganic layer was separated and washed with water followed by brine.Drying of the organic layer over Na₂SO₄ and evaporation of the solventgave a light yellow solid. This was suspended in acetone and the mixturebrought to reflux and then allowed to stand at room temperatureovernight. Filtration of the solid and concentration of the filtrategave a solid that was subjected to column chromatography (toluene:hexane3:7) to give4-[9,9-dioctyl-7-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9H-fluoren-2-yl]-N,N-diphenylaniline.

Example 13

[0328] Synthesis of2-{7-[3,5-Bis(trifluoromethyl)phenyl]-9,9-dioctyl-9H-fluoren-2-yl}-4,4,5,5-tetramethyl-1,3,2-dioxaborolaneand 2,7-Bis[3,5-bis(trifluoromethyl)phenyl]-9,9-dioctyl-9H-fluorene

[0329] 3,5-Bistrifluoromethylbromobenzene (0.293 g, 1 mmole, 1 equiv),2-[9,9-dioctyl-7-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9H-fluoren-2-yl]-4,4,5,5-tetramethyl-1,3,2-dioxaborolane(1.28 g, 2 mmole, 2 equiv), Aliquat™ 336 (tricaprylylmethylammoniumchloride) (0.15 g, 0.375 mmole, 0.25 eq) and 2M sodium carbonatesolution (1.25 mL, 2.5 mmole, 2.5 eq) were added to 10 mL of toluene.This was purged with a stream of nitrogen for about 30 min. Under anitrogen purge, tetrakis(triphenylphosphine) palladium (0) (14 mg, 0.012mmole, 0.012 eq) was added. The reaction mixture was then refluxed for16 hrs. The reaction was cooled to room temperature and water added. Theorganic layer was separated and washed with water, followed by brine.Drying of the organic layer over Na₂SO₄ and evaporation of the solventgave a light yellow solid. The solid was dissolved in ether, and a smallportion of it was applied on a silica thin layer chromatography (TLC)plate. The TLC plate was eluted with 1:1 toluene:hexane to give threedistinctive bands. The middle band was collected and was determined tobe2-{7-[3,5-bis(trifluoromethyl)phenyl]-9,9-dioctyl-9H-fluoren-2-yl}-4,4,5,5-tetramethyl-1,3,2-dioxaborolaneobtained as a light yellow oil (28 mg). ¹H NMR: δ0.53-0.69 (m, 4H), 0.78(t, 6H), 0.96-1.29 (m, 20H), 1.40 (s, 12H), 1.97-2.11 (m, 4H), 7.52, (s,1H), 7.56 (d, 1H), 7.72-7.80 (m, 2H), 7.80-7.88 (m, 3H), 8.05 (s, 2H).The band having the greatest elution distance was collected and wasdetermined to be the by-product2,7-bis[3,5-bis(trifluoromethyl)phenyl]-9,9-dioctyl-9H-fluoreneobtained, as a light yellow oil (8 mg). ¹H NMR: δ0.51-0.65 (m, 4H), 0.70(t, 6H), 0.91-1.26 (m, 20H), 1.98-2.11 (m, 4H), 7.49,(s, 2H), 7.56 (d,2H), 7.80 (d, 4H), 8.00 (s, 4H).

Example 14

[0330] Synthesis of 2-Bromo-9,9-bis(3,6-dioxahexyl-6-phenyl)-fluorene

[0331] 2-Bromo-9,9-bis(3,6-dioxahexyl-6-phenyl)-fluorene was synthesizedfrom PhO(CH₂)₂O(CH₂)₂I and 2-bromofluorene following the procedureessentially as described in Example 9.

Example 15

[0332] Synthesis of2-(4-Chlorophenyl)-5-(2-methoxyphenyl)-1,3,4-oxadiazole

[0333] By the general method for the synthesis of2-(2,5-dibromophenyl)-5-[4-(octyloxy)phenyl]-1,3,4-oxadiazole (1) inExample 3, the reaction of 4-chlorobenzoyl chloride (43.22 g, 0.247mole) with 2-methoxybenzoyl hydrazide (41.10 g, 0.247 mole) gave theintermediate N′-(4-chlorobenzoyl)-2-methoxybenzohydrazide (54.38 g, 72%yield). Cyclocondensation ofN′-(4-chlorobenzoyl)-2-methoxybenzohydrazide (30.0 g, 0.098 mole) withPOCl₃ (250 mL) gave2-(4-chlorophenyl)-5-(2-methoxyphenyl)-1,3,4-oxadiazole (23.44 g, 82%yield).

[0334] Electroactive Polymeric Arylenes

Example 16

[0335] Polymerization and End Capping of2-(2,5-Dichlorophenyl)-5-[4-(octyloxy)phenyl]-1,3,4-oxadiazole

[0336] Into a flask fitted with a septum and nitrogen purge wasintroduced 4.10 g (9.77 mmol) of2-(2,5-dichlorophenyl)-5-[4-(octyloxy)phenyl]-1,3,4-oxadiazole (2) fromExample 1, 2.85 g (10.89 mmol) of triphenylphosphine, and 0.31 g (1.421mmol) of anhydrous nickel (II) bromide. To this was added 75 ml dry DMFand 25 ml dry toluene. This was azeotroped with the use of a Dean-Starkcondenser followed by distilling off much of the toluene. To the cooledreaction solution was added a further 0.31 g (1.421 mmol) of anhydrousnickel (II) bromide under a strong nitrogen purge. This was heated at80° C. for 30 minutes followed by the addition of 1.0 g chlorobenzene asend-capping agent. The reaction was allowed to proceed for 8 hours at80° C. The cooled reaction mixture was poured into about 500 ml acetoneand filtered. The solid cake was taken up in methylene chloride and 1NHCl added and the two phase system stirred for about an hour. Theresulting solids were filtered off and the filtrate transferred to aseparatory funnel. The lower organic layer was separated and poured intoan excess of methanol. The solid was collected, washed with methanol anddried to give 2.8 g of polymer. Gel permeation chromatograpy (GPC) wasrun on this polymer and on polymers made in succeeding Examples asfollows.

[0337] GPC sample was prepared by the addition of 10.0 ml oftetrahydrofuran to approximately 25.0 mg of sample. After shakingovernight, the solution was filtered (ACRODISC CR 25 mmpoly(tetrafluoroethylene) syringe filter with 25 micron pores, GelmanLaboratory, Ann Arbor, Mich.). 150 Microliters of the solution wasinjected into a two column set (mixed bed and 500A columns, JordiAssociates, Bellingham, Mass.) by a Waters 150-C chromatograph (WatersCorp., Milford, Mass.). The 150-C operated at room temperature usingtetrahydrofuran as the eluent, flowing at a rate of 1.0 min. Changes inconcentration were detected by the 150-C's internal refractive indexdetector. The molecular weight calculations were based upon acalibration made of narrow dispersity polystyrenes ranging in molecularweight from 7.5×10⁶ to 580. The actual calculations were completed withCALIBER software from Polymer Laboratories, Amherst, Mass.

[0338] GPC analysis gave a weight average molecular weight (Mw) of2.49×10⁴, a number average molecular weight (Mn) of 8.40×10³ and apolydispersity (PD) of 2.97.

[0339] A MALDI/TOF mass spectrum was obtained by using the PerSeptiveBiosystems DE-STR MALDI/TOF mass spectrometer (matrix ssisted laserdesorption ionization time-of-flight mass spectrometer) (available fromPerSeptive Biosystems, Inc., Framingham, Mass.) in both the linear andreflectron detection modes. The sample was prepared in 10 mg/mltetrahydrofuran solvent solution. Dithranol (1,8,9-anthracenetriol) wasutilized as the MALDI matrix. Approximately 40 microliters of matrix wasmixed with 10 microliters of analyte solution. The positive-ionMALDI/TOF mass spectrum contained a series of peaks separated by 348Daltons and with an absolute molecular weight that corresponded topolymer termination by phenyl groups. Close examination of the narrowmass range clearly showed the presence of two other series of peaks fromsequential replacement of the phenyl group with hydrogen. The followingproducts were found:

[0340] The reflection detector was able to observe an oligomerdistribution were n was up to 15, and the linear detector was able toobserve an oligomer distribution were n was from 2 to 22.

[0341] The emission spectrum of the above polymer was run and comparedto that of the corresponding monomer,2-(phenyl)-5-[4-(octyloxy)phenyl]-1,3,4-oxadiazole. The results in FIG.5 show that the emission maximum of the polymer at 419 nm wassignificantly red-shifted relative to the emission maximum of themonomer at 376 nm.

Example 17

[0342] Polymerization and End Capping of2-(2,5-Dibromophenyl)-5-[4-(octyloxy)phenyl]1,3,4-oxadiazole

[0343] A 500 ml round bottomed flask fitted with a magnetic stir-bar andrubber septum was put in a nitrogen filled glove box and was chargedwith 7.47 g (0.0272 mol) of bis(1,5-cyclooctadiene)nickel(0) and 4.24 g(0.0272 mol) 2,2′-bipyridyl. The sealed flask was then transferred to afume hood and 26 ml of dry DMF and 65 ml toluene added via a cannula.The flask was then heated at 80° C. for 30 min. in an oil bath. Asolution of 6.0 g (0.0118 mol)2-(2,5-dibromophenyl)-5-[4-(octyloxy)phenyl]-1,3,4-oxadiazole (1) fromExample 3 in about 15 ml toluene was added via a cannula. The sealedflask was heating for five minutes at 80° C., followed by the additionof 1.74 ml (1.53 g; density 0.882 g/ml; 0.0142 mol) of1,5-cyclooctadiene. Heating was continued at 80° C. for 24 hrs. To thereaction flask was then added 1 mL of dry bromobenzene and heatingcontinued at 80° C. for 24 hrs.

[0344] To the warm mixture was added 150 ml of chloroform and stirringcontinued for 30 min. The content of the flask was then extracted with2N HCl (2×200 mL). The organic layer was washed with sodium carbonatesolution and dried with magnesium sulfate. The product was precipitatedinto methanol and dried to give 3.0 g of a fibrous polymer. GPC analysisof the polymer gave a weight average molecular weight (Mw) of 9.1×10⁴, anumber average molecular weight (Mn) of 1.02×10⁴, and a polydispersity(PD) of 8.93.

Example 18

[0345] Polymerization and End Capping of2-(4-tert-Butylphenyl)-5-(2,5-dichlorophenyl)-1,3,4-oxadiazole

[0346] Into a flask fitted with a septum and nitrogen purge wasintroduced 2.50 g (7.2 mmol) of2-(4-tert-butylphenyl)-5-(2,5-dichlorophenyl)-1,3,4-oxadiazole (3) fromExample 2, 0.81 g (7.2 mmol) chlorobenzene, 2.90 g (11.03 mmol) oftriphenylphosphine, and 0.31 g (1.421 mmol) of anhydrous nickel (II)bromide. To this was added 75 ml dry DMF and 25 ml dry toluene. This wasazeotroped with the use of a Dean-Stark condenser followed by distillingoff much of the toluene. To the cooled reaction solution under a strongnitrogen purge was added a further 0.31 g (1.421 mmol) of anhydrousnickel (II) bromide. This was heated at 80° C. for 12 hours. The cooledreaction mixture was diluted with methylene chloride and filtered. Thefiltrate was stirred with 1N HCl for about an hour and then transferredto a separatory funnel. The lower layer was separated, washed with waterand then poured into an excess of methanol. The solid was collected,washed with methanol and dried to give the required product. GPCanalysis gave a Mw of 1.70×10⁴, a Mn of 1.50×10³, and a PD of 1.11. Thepositive ion MALDI/TOF mass spectrum obtained from this sample showed anoligomer distribution range from n=3 to n=32 around 6500 daltons. Closeexamination of the narrow mass range showed that the end-groups includedsome hydrogen as well as phenyl groups.

[0347] The emission spectrum of the above polymer was run and comparedto that of a similar monomer,2-(phenyl)-5-[4-(octyloxy)phenyl]-1,3,4-oxadiazole. The results in FIG.5 show that the emission maximum of the polymer at 419 nm wassignificantly red-shifted relative to the emission maximum of themonomer at 376 nm.

Example 19

[0348] Polymerization and End Capping of2-(2,5-Dichlorophenyl)-5-(9,9-dioctyl-9H-fluoren-2-yl)-1,3,4-oxadiazole

[0349] Into a 500 mL flask was charged2-(2,5-dichlorophenyl)-5-(9,9-dioctyl-9H-fluoren-2-yl)-1,3,4-oxadiazole(13) from Example 5, nickel (II) bromide (0.67 g, 3.05 mmole),triphenylphosphine 6.14 g, 23.4 mmole), dry toluene and DMF. This washeated at 80° C. under nitrogen for 30 min. Zinc (6.19 g, 94.7 mmole)and nickel (II) bromide (0.67 g, 3.05 mmole) were added under a nitrogenpurge. Heating was continued for 12 hours at 80° C. Bromobenzene (2 mL)was added as a capping agent and heating continued for two days. Thecooled reaction mixture was diluted with methylene chloride andfiltered. The filtrate was stirred with 1N HCl and the organic layerseparated. Precipitation into methanol gave the desired polymer as afibrous white solid. GPC analysis gave: Mw =1.03×10⁵, Mn=3.8×10⁴,PD=2.67.

Example 20

[0350] Copolymerization of1,4-Bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-phenyl and2-(2,5-Dibromophenyl)-5-[4-octyloxy)phenyl]-1,3,4-oxadiazole

[0351] 1,4-Bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-phenyl(6.6g, 20 mmole), made by reaction of benzene-1,4-bis(boronic acid) withpinacol, and2-(2,5-dibromophenyl)-5-[4-octyloxy)phenyl]-1,3,4-oxadiazole (1)(8.856g, 18 mmole) from Example 3 are mixed together with Aliquat™ 336(tricaprylylmethylammonium chloride) (2.02 g, 5 mmole) in 212 mLtoluene. To the resulting suspension is added 36 mL of 2M aqueous Na₂CO₃solution and the mixture is then purged with nitrogen for one hour.Tetrakis(triphenylphosphine)palladium (0) (0.232g, 0.2 mmole) is thenadded under nitrogen. The reaction is refluxed under nitrogen for 3days. 1 mL of bromobenzene is added and the reaction further refluxedfor 18 hours. After the reaction is cooled down, it is poured to 500 mLof methanol and water (9:1). The polymer precipitates out as rubberyglue-like semi solid. The solid is filtered and dried under suction. Thecake is redissolved in chloroform and precipitated from methanol. Theprecipitate is filtered and washed with methanol to give a solid.

Example 21

[0352] Preparation of a Poly(carbazole-co-phenylene) Block-Copolymer

[0353] Part A

[0354] Synthesis of9-Phenyl-3,6-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9H-carbazole

[0355] A 2L flask was charged with 600 mL dry THF and3,6-dibromo-9-phenylcarbazole (60 g, 0.15 mole). This was cooled to −78°C. with an acetone-dry ice bath. n-Butyllithium (138 mL of a 2.5Msolution in hexanes, 0.34 mole) was added drop-wise via syringe. Thereaction was stirred for 20 minutes and then warmed to −50° C. Thetemperature was reduced to −78° C. and2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (64 g, 0.34 mole)added via syringe at such a rate as to maintain the temperature below−60° C. The temperature was maintained at −78° C. for two hours and thenpoured into an aqueous solution of ammonium acetate (90 g in 2100 mLwater). The layers were phase separated and the aqueous phase extractedwith methy tert-butyl ketone (2×200 mL). The combined organic phase andextracts were washed with brine (2×200 mL) and dried over magnesiumsulfate. Concentration and re-crystallization of the resulting solidfrom acetone gave pure9-phenyl-3,6-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9H-carbazole(PBTDC).

[0356] Part B

[0357] Preparation of Borolane Terminated Poly(9-phenylcarbazole)Pre-polymers

[0358] The reaction of PBTDC from Part A, 2M Na₂CO₃ (42.4 g), Aliquat™336 (tricaprylylmethylammonium chloride) (1.28 g) and3,6-dibromo-9-phenylcarbazole (DBPC) in 100 mL toluene under standardSuzuki coupling conditions using the amounts of PBTDC and DBPC shown inTable 1 gave oligomers with 8.75 and 2.75 repeat units, respectively, asdetermined by NMR spectroscopy. Standard Suzuki coupling conditions andwork-up included a nitrogen purge, addition oftetrakis(triphenylphosphine) palladium (0) (0.06 g), refluxing for 12hours, pouring the resulting cooled reaction mixture into water,separating and extracting the organic layer with methylene chloride, andpouring the combined orgainic layers into about 500 mL of methanol toprecipitate the solid product. TABLE 1 Oligomer Repeat Units as aFunction of Reactant Amounts. PBTDC DBPC PBTDC/ monomer monomer DBPCmolar Pre-polymer Number of (g) (g) ratio Yield (g) Repeat Units 7.413.0 2:1 2.05 8.75 11.1 3.0 3:1 3.82 2.75

[0359] Part C

[0360] Preparation of a Poly(carbazole-co-phenylene) Block-Copolymer

[0361] Into a 250 mL flask fitted with a reflux condenser, nitrogeninlet and rubber septum was added the pre-polymer of Part B (2.72 g, 2.9mmole, 3 equiv),2-(2,5-dibromophenyl)-5-[4-(ocyloxy)phenyl]-1,3,4-oxadiazole (1) (2.50g, 4.92 mmole, 5 equiv), sodium carbonate (16.72 mL of a 2M aqueoussolution, 33.4 mmole), Aliquat™ 336 and toluene. The stirred mixture waspurged with a stream of nitrogen for an hour and then for 30 minutes at50° C. Under a nitrogen purge, tetrakis(triphenylphosphine) palladium(0) (0.0244 g, 0.0211 mmole) was added. The content of the flask wasrefluxed for 12 hrs. The cooled reaction mixture was poured into water,and the organic layer was separated. The aqueous layer was extractedwith methylene chloride. The combined orgainic layers were poured intoabout 500 mL of methanol to precipitate a solid. This was filtered off,washed with methanol and dried to give 1.21 g of the desired polymer.

[0362] Part D

[0363] The polymer from Part C is combined successively with an excessof phenyl boronic acid under standard Suzuki coupling conditions(refluxing toluene/2M aqueous sodium carbonate) and then an excess ofbromobenzene with heating to provide the phenyl capped polymer.

Example 22

[0364] Polymerization of2-(2,5-Dibromophenyl)-5-[4-(octyloxy)phenyl]1,3,4-oxadiazole and EndCapping with Fluorene

[0365] The polymerization is carried out as in Example 17. A 500 mlround bottomed flask fitted with a magnetic stir-bar and rubber septumwas put in a nitrogen filled glove box and is charged with 7.47 g(0.0272 mol) of bis(1,5-cyclooctadiene)nickel(0) and 4.24 g (0.0272 mol)2,2′-bipyridyl. The sealed flask is then transferred to a fume hood and26 ml of dry DMF and 65 ml toluene added via a cannula. The flask isthen heated at 80° C. for 30 min. in an oil bath. A solution of 6.0 g(0.0118 mol)2-(2,5-dibromophenyl)-5-[4-(octyloxy)phenyl]-1,3,4-oxadiazole (1) fromExample 3 in about 15 ml toluene is added via a cannula. The sealedflask is heating for five minutes at 80° C., followed by the addition of1.74 ml (1.53 g; density 0.882 g/ml; 0.0142 mol) of 1,5-cyclooctadiene.Heating is continued at 80° C. for 24 hrs. To the reaction flask is thenadded 1 g of dry 2-bromo-9,9-dioctylfluorene and heating continued at80° C. for 24 hrs.

[0366] To the warm mixture is added 150 ml of chloroform and stirringcontinued for 30 minutes. The content of the flask is then extractedwith 2N HCl (2×200 mL). The organic layer is washed with sodiumcarbonate solution and dried with magnesium sulfate. The product isprecipitated into methanol and dried to give 3.0 g of polymer. GPCanalysis of the polymer gives a weight average molecular weight (Mw) ofabout 1×10⁵.

Example 23

[0367] Preparation of a Blue-Emitting Polyfluorene Containing 30 MolePercent of Electron Transport Oxadiazole

[0368]2,7-Bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9,9-dioctyl-fluorene(5.38 g, 8.37 mmole), 2,7-dibromo-9,9-dioctylfluorene (1.80 g, 3.28mmole) and 2-(2,5-dibromophenyl)-5-[4-(octyloxy)phenyl]-1,3,4-oxadiazole(1) from Example 3 (2.50 g, 4.92 mmole) were mixed together withAliquat™ 336 (tricaprylylmethylammonium chloride) (0.0.85 g, 2.09mmole,) in 150 mL toluene. To this was added 28 mL of an aqueous 2MNa₂CO₃ solution, and the resulting mixture was then degassed withnitrogen for 2 hours at room temperature and then at 50° C. for afurther 2 hours. Tetrakis(triphenylphosphine)palladium (0) (0.04 g,0.035 mmole) was then added to the mixture. The resulting mixture washeated at reflux under nitrogen for 16 hours. A nitrogen purged solutionof 1 mL bromobenzene in toluene was added followed by a further chargeof 0.04 g of tetrakis(triphenylphosphine)palladium (0), and theresulting mixture was then refluxed for another 16 hrs. After thereaction mixture was cooled to room temperature, it was poured into 2Lmethanol and the precipitate collected by filtration. The precipitatewas purified by repeated dissolution in methylene chloride and thenprecipitation in methanol. The product was obtained as 5.4 g of a lightpowder. Gel permeation chromatography analysis of the product gave:Mw=7.30×10⁴, Mn=2.36×10⁴, and PD=3.09. Proton NMR of the polymersupported the expected 30 mole percent content of theoxadiazole-containing monomer unit.

[0369] To provide a lower molecular weight polymer the above wasrepeated except that amount of2,7-bis(4,4,5,5-tetrametbyl-1,3,2-dioxaborolan-2-yl)-9,9-dioctyl-fluoreneused was increased to 5.85 g. The product, obtained as 4.8 g of powder,was analyzed by gel permeation chromatography and differential scanningcalorimetry (DSC), and the results are given in Table 2.

Example 24

[0370] Preparation of a Green-Emitting Polymer Containing 10 MolePercent of Electron Transport Oxadiazole

[0371]2,7-Bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9,9-dioctyl-fluorene(4.84 g, 7.53 mmole, 5.1 eq), 4,7-dibromo-2,1,3-benzothiadiazole (1.74g, 5.90 mmol) and2-(2,5-dibromophenyl)-5-[4-(octyloxy)phenyl]-1,3,4-oxadiazole (1) fromExample 3 (0.75 g, 1.48 mmole) were mixed together with Aliquat™ 336(tricaprylylmethylammonium chloride) (0.76 g, 1.86 mmole) in 150 mLtoluene. To this was added 28 mL of an aqueous 2M Na₂CO₃ solution, andthe mixture was then degassed with nitrogen for 2 hours at roomtemperature and then at 50° C. for a further 2 hours.Tetrakis(triphenylphosphine)palladium (0) (0.04 g, 0.035 mmole) was thenadded to the mixture. The resulting mixture was heated at reflux undernitrogen for 16 hours. A nitrogen purged solution of 1 mL bromobenzenein toluene was added followed by a further charge of 0.04 g oftetrakis(triphenylphosphine)palladium (0), and the resulting mixture wasrefluxed for another 16 hrs. After the reaction mixture was cooled toroom temperature, it was poured into 2L methanol, and the resultingprecipitate was collected by filtration. The precipitate was purified byrepeated dissolution in methylene chloride and precipitation inmethanol. The product was obtained as 3.95 g of a light yellow-greenpowder. Gel permeation chromatography analysis of the product gave:Mw=2.19×10⁴, Mn=7.49×10³, PD=2.93.

Example 25

[0372] Preparation of a Terpolymer Containing Hole and ElectronTransport Functionality

[0373] 2,7-Dibromo-9,9-dioctylfluorene (1.00 g, 1.82 mmole, 1 eq),2,7-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9,9-dioctyl-fluorene(5.98 g, 9.30 mmole, 5.1 eq), 3,6-dibromo-9-phenylcarbazole (1.46 g,3.65 mmole, 2 equiv) and2-(2,5-dibromophenyl)-5-[4-(octyloxy)phenyl]-1,3,4-oxadiazole (1) fromExample 3 (1.85 g, 3.65 mmole, 2 eq) were mixed together with Aliquat™336 (tricaprylylmethylammonium chloride) (0.94 g, 2.32 mmole, 1.275equiv) in 150 mL toluene. To this was added 31.5 mL of an aqueous 2MNa₂CO₃ (62 mmole, 34 equiv) solution and the mixture then degassed withnitrogen for 2 hrs at room temperature and then at 50° C. for a further2 hours. Tetrakis(triphenylphosphine)palladium (0) (0.05 g, 0.039 mmole)was then added to the mixture. The resulting mixture was heated atreflux under nitrogen for 16 hours. A nitrogen purged solution of 1 mLbromobenzene in toluene was added followed by a further charge of 0.039g of tetrakis(triphenylphosphine)palladium (0), and the resultingmixture was then refluxed for another 16 hrs. After the reaction mixturewas cooled to room temperature, it was poured to 2L methanol, and theprecipitate was collected by filtration. The precipitate was purified byrepeated dissolution in methylene chloride and precipitation inmethanol. The resulting product was obtained as 5.2 g of a grayishpowder. GPC and DSC data are given in Table 2.

Example 26

[0374] Preparation of a Blue-Emitting Polyfluorene Containing 10 MolePercent of Electron Transport Oxadiazole

[0375] A blue-emitting polyfluorene containing 10 mole percent ofelectron transport oxadiazole was prepared essentially as described inExample 23. Thus, the polymerization of the monomers2,7-dibromo-9,9-dioctylfluorene (6.0 g, 10.94 mmol, 0.8 equiv),9,9-dioctyl-2,7-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-fluorene(8.83 g, 14.003 mmol, 1.024 equiv),2-(2,5-dibromophenyl)-5-[4-(octyloxy)phenyl]-1,3,4-oxadiazole (1.39 g,2.735 mmol, 0.2 equiv), in toluene (112 ml) with and 2M Na₂CO₃ (27.35ml, 54.7 mmol) and Aliquat™ 336 (tricaprylylmethylammonium chloride) forabout 24 hours gave, after phenyl-capping, a polymer for which gelpermeation chromatogaraphy gave: Mw=9.0×10⁴, Mn=2.65×10⁴, and PD=3.40.

[0376] Comparative Example C1

[0377] Synthesis of a Medium Molecular Weight Phenyl Capped9,9′-Dioctylfluorene Homopolymer

[0378] A medium molecular weight 9,9′-dioctylfluorene homopolymer wasprepared by Suzuki coupling methods according to the literatureprocedures outlined in J. Chem. Soc. Chem. Commun. 1597-1598 (1997). Thepolymer was then capped by reaction with bromobenzene as in Example 23.Gel permeation chromatograpy of the resulting polymer gave: Mw=44,900,Mn=17,400, and PD=2.58. GPC and DSC data are given in Table 2.

Comparative Example C2

[0379] Synthesis of a High Molecular Weight Phenyl Capped9,9′-Dioctylfluorene Homopolymer

[0380] This polymer was prepared by Yammamoto coupling as follows. A 1Lround bottomed flask fitted with a magnetic stir-bar and rubber septumin a nitrogen glove box was charged with 28.84 g (0.1048 mol) ofbis(1,5-cyclooctadiene)nickel(0) and 16.37 g (0.1484 mol)2,2′-bipyridyl. The sealed flask was then transferred to a fume hood and103 ml of dry DMF and 250 ml toluene added via a cannula. The flask wasthen heated at 80° C. for 30 min. in an oil bath. A solution of 25.0 g(0.04558 mol) 2,7-dibromo-9,9-dioctylfluorene in about 40 ml toluene wasadded via a cannula. The sealed flask was heating for five minutes at80° C. followed by the addition of 6.7 ml (5.92 g; density 0.882 g/ml;0.0186 mol) of 1,5-cyclooctadiene. Heating was continued at 80° C. for 4days. To the reaction flask was added 3 ml of dry bromobenzene andheating continued at 80° C. for 24 hours.

[0381] To the warm mixture was added 300 ml of chloroform and stirringcontinued for 30 min. The content of the flask was then extracted with2N HCl (2×200 ml). The organic layer was washed with sodium carbonatesolution and dried with magnesium sulfate. The product was precipitatedin methanol and dried to give 15.8 g of phenyl cappedpoly(9,9-di-n-octylfluorene-2,7-diyl). GPC analysis gave: Mw=374,000,Mn=127,000, and PD=2.94. GPC and DSC data are given in Table 2. TABLE 2DSC and GPC Data for Polyfluorenes and Fluorene-Oxadiazole Copolymers.Polymer M_(w) (×10⁻³) M_(n) (×10⁻³) PD T_(g) (° C.) T_(c) (° C.) T_(m)(° C.) Comp. Ex. C1 44.9 17.4 2.58 59.2 76.4 146.6 Comp. Ex. C2 374 1272.94 75.6 90.1 150 Example 23 21.3 8.51 2.50 62 none none Example 2530.9 10.5 2.95 106.1 none none Example 26 90.0 26.5 3.40 68.3 none none

[0382] Table 2 shows Differential Scanning Calorimetry (DSC) and GelPermeation Chromatography (GPC) data for the two comparative9,9′-dioctylfluorene homopolymers of Comparative Examples C1 and C2, the9,9′-dioctylfluorene-phenyl oxadiazole copolymers having 10% phenyloxadiazole monomer units (Example 26) and having 30% phenyl oxadiazolemonomer units (Example 23), as well as the 9,9′-dioctylfluorene-phenyloxadiazole-phenyl carbazole terpolymer (Example 25).

[0383] The 9,9′-dioctylfluorene homopolymers of Comparative Examples C1and C2 exhibited glass transition temperatures of T_(g)=59.2 and 75.6°C., respectively. On heating above the glass transition temperature,both polymers exhibit crystallization and melt transitions, as shown inTable 2. These types of transitions indicated a thermal instability ofamorphous films of these polymers (i.e. a propensity to undergoformation of crystalline domains that can lead to excimer formation andcolor shifting). Both of these polymers exhibited color shifting fromblue to green in both the photoluminescence and electroluminescencespectrum upon accelerated thermal aging of thin spin cast films of thepolymers.

[0384] Table 2 shows that the phenyl oxadiazole containing polymers ofExamples 23, 25, and 26 have molecular weights of Mw=21,300, Mw=30,900,Mw=90,000, respectively, and polydispersities that are comparable tothose obtained for the 9,9′-dioctylfluorene homopolymers of ComparativeExamples C1 and C2. The glass transition temperatures of the copolymersof Examples 23 and 26 (Tg=62° C. and Tg=68.3° C., respectively)suggested that incorporation of the phenyl oxadiazole comonomer into thepolyfluorene polymer did not greatly affect the Tg compared with thoseobtained for the 9,9′-dioctylfluorene homopolymers. The glass transitiontemperature for the terpolymer of Example 25 (Tg=106.1° C.) suggestedthat incorporation of the phenyl carbazole comonomer into the polymerincreased Tg considerably.

[0385] Table 2 also shows that none of the phenyl oxadiazole-containingpolymers of Examples 23, 25, and 26 exhibited crystallization and melttransitions, which were observed for the 9,9′-dioctylfluorenehomopolymers. Instead, the phenyl oxadiazole containing polymersremained amorphous above the glass transition temperature. This is animportant discovery, especially since these new phenyloxadiazole-containing polymers do not exhibit excimer emission (colorshifting) during accelerated aging, as described in Example 27.

Example 27

[0386] Accelerated Aging Studies for Polyfluorene-Phenyl OxadiazoleCopolymers and Comparison to Polyfluorene Homopolymers

[0387] Polyfluorene-phenyl oxadiazole copolymers of Examples 23, 25, and26 were separately dissolved in dry toluene to final concentrations of1% by weight of the solution. These solutions were spin coated ontoseparate 2 cm×2 cm quarts slides at a spin rate of 2500 rpm.Photoluminescence spectra for each the thin films were measured in afront face mode on a Spex Fluorolog fluorimeter (Spex Industries,Edison, N.J.). Each slide was then placed face up on a heating plate andcovered with a nitrogen purged glass dome that maintained a steady flowof nitrogen gas over the samples. The samples were heated under nitrogento 200° C. for 15 hours. The photoluminescence spectrum for each filmwas then remeasured.

[0388]FIG. 6 shows the photoluminescence as a function of wavelength ofspin coated thin films of the copolymer of Example 23 (polyfluorenecontaining 30 mole percent of phenyl oxadiazole units) before (emissionspectum 402) and after (emission spectrum 400) thermal annealing under anitrogen purge at 200° C. for 15 hours. The same tests were run on thecopolymers of Examples 25 and 26 The intensity and wavelength of theemission was substantially the same before and after annealing. Thiscontrasts the blue to green color shifting observed for correspondingfilms of the phenyl capped 9,9′-dioctylfluorene of Comparative ExamplesC1 and C2. For these polymers, annealing of thin films gives rise togrowth of strong green emission centered at 520 nm. These resultsindicate that incorporation of the phenyl oxadiazole comonomer intopoly(9,9′-dioctylfluorenes) stabilized the polymers with respect tocrystallization and/or excimer formation. This is important, especiallyfor achieving a stable blue light emitting OLED device.

[0389] Electroactive Compositions and Organic Electroluminescent Devices

Examples 28-46

[0390] Compositions and Electoluminescent Devices Based on PhenylOxadiazole Homopolymers

[0391] Electroactive compositions were prepared as follows: The polymersof Examples 16, 18, and 19 were independently dissolved at 1-3 wt/wt %into dichloroethane or toluene (HPLC grade obtained from AldrichChemical, Milwaukee, Wis.). A hole transporting agent (HTA) selectedfrom TPD, NPB, CBP, and HT were added in a ratio of polymer/HTA=10:3; insome cases 10:6, 10:12 or 10:18. Molecular emitters perylene, TMC,Ir(ppy)₃, (bthpy)₂Ir(acac), and Pt(OEP) were introduced in amounts of0.01-0.5 wt/wt % by addition of small aliquots of a 10 mM solution ofthe emitter in dichloroethane (DCE). Each coating solution was filteredthrough a 0.45 μm polypropylene syringe filter before application.

[0392] Organic electroluminescent devices were constructed as follows:Glass squares of 2 cm×2 cm having on one side a vapor deposited coatingof indium tin oxide (ITO) were obtained from Thin Film Devices (Anaheim,Calif.). The ITO coated sides were cleaned with ethanol, treated with anO₂ plasma etch (4 min at 50 W and 200 mTorr), treated by spin coating(2500 rpm for 30 sec) of an aqueous solution of PEDT/PSS copolymer anddried under nitrogen purge at 115° C. Next, the coating solutionsprepared above were each spin coated on top of a PEDT/PSS coatedsubstrate (2500 rpm for 30 sec). The glass squares were then mountedinto an aluminum frame, introduced into a vacuum deposition chamber, andpumped to 10⁻⁶ torr for about 1 hour. Cathodes were applied by vapordepositing about 10 Å of LiF and about 2000 Å of aluminum.

[0393] The resulting organic electroluminescent lamps were evaluated fordrive voltages (V), external percent quantum efficiencies (% Q.E.),luminescence intensities (cd/m²), and ion maxima (δ_(max) nm) for blue,green, and red lamps operating at 20 mA/cm² drive t. Table 3 summarizesthe electroactive compositions and results of the respectiveevaluations. The materials in the electroactive compositions arerecorded in Table 3 e number of parts (p) by weight added to 1000 parts(1000 p) DCE to make the spin ng solution used in preparing the lamps.TABLE 3 Electroactive Compositions and Lamp Evaluation Results p HTA/Electroluminescence data at p Polymer/ 1000 p p Emitter/ 20 mA/cm² 1000p DCE DCE 1000 p DCE voltage % λ_(max) Example (Polymer) (HTA) (Emitter)(V) Q.E. cd/m² nm 28 10 (Ex. 18) 3 (TPD) 0.085 (Ir(ppy)₃) 4.9 0.84 590513 29 10 (Ex. 18) 3 (TPD) 0.094 5.1 0.37 42 650 (Pt(OEP)) 30 10 (Ex.16) 3 (TPD) 0.094 7.7 1.1 92 648 (Pt(OEP)) 31 10 (Ex. 16) 3 (CBP) 0.0949.7 1.0 92 650 (Pt(OEP)) 32 10 (Ex. 16) 3 (TPD) 0.085 (Ir(ppy)₃) 7.4 2.01400 513 33 10 (Ex. 16) 3 (CBP) 0.085 (Ir(ppy)₃) 6.2 2.7 1900 513 34 10(Ex. 16) 3 HT 0.085 (Ir(ppy)₃) 8.3 1.42 1040 514 35 10 (Ex. 16) 12 (CBP)0.085 (Ir(ppy)₃) 7.1 3.4 2300 513 36 10 (Ex. 16) 18 (CBP) 0.085(Ir(ppy)₃) 8.1 5.3 3700 513 37 10 (Ex. 16) 3 (CBP) none 12.4 0.38 73 44438 10 (Ex. 16) 6 (CBP) none 8.8 0.26 37 437 39 10 (Ex. 16) 12 (CBP) none5.5 0.11 7.3 414 40 10 (Ex. 16) 3 (CBP) 0.033 (TMC) 7.9 0.42 64 435 4110 (Ex. 16) 3 (CBP) 0.039 5.0 0.28 72 455, (perylene) 482 42 10 (Ex. 16)6 (CBP) 0.078 5.8 0.39 98 455, (perylene) 482 43 10 (Ex. 16) 3 (CBP)0.085 6.1 0.43 88 615, (bthpy)₂Ir(acac) 669 44 10 (Ex. 19) 3 (CBP) 0.085(Ir(ppy)₃) 9.1 0.39 152 515 45 10 (Ex. 19) 3 (HT 0.085 (Ir(ppy)₃) 8.40.30 207 516 polymer) 46 10 (Ex. 19) 3 (TPD) 0.085 (Ir(ppy)₃) 6.7 0.21152 513

[0394] The results in Table 3 show that light was observed from each ofthe organic electroluminescent lamp devices of Examples 28-46, and eachdevice provided diode type behavior. The polymer of Example 16 inconjunction with the hole transport agent CBP yielded blue emission inthe absence of added emitter (Example 37). Increasing the CBP contentlead to a larger background current and a decline in external quantumefficiency (Examples 37-39). Doping of the polymer/HTA blends withvarious blue emitters such as perylene and 3-thienyl-7-methoxycoumarin(TMC) gave blue emission. Doping with Ir(ppy)3 gave green emission.Doping with Pt(OEP) or with (bthpy)₂Ir(acac) gave red emission. In allcompositions, low operating voltages and acceptable quantum efficiencieswere achieved.

[0395] While not wishing to be bound by theory, the high quantumefficiencies of the Ir(ppy)₃ doped lamps (Examples 32-36) can beunderstood in terms of the HOMO and LUMO energy matching of theelectroactive polymeric arylene of Example 16, CBP, and Ir(ppy)₃. Thepolymer of Example 16 is an efficient electron transport polymer with aLUMO level that matches up well with the LUMO for Ir(ppy)₃. Likewise,CBP is an efficient hole transport agent with a HOMO that matches wellwith the HOMO of Ir(ppy)₃. Finally, the polymer of Example 16 has such adeep HOMO at 6.3 eV that it cannot readily transport holes or serve as asite for exciton formation. Energetically, CBP can support excitonformation and emission, as seen in lamps having no dopant, but thestrong match of both the HOMO and LUMO levels of both CBP and Ir(ppy)₃allows efficient formation or migration of excitons to Ir(ppy)₃. Also,emission from CBP overlaps the absorption band of Ir(ppy)₃ leading toefficient energy transfer and reemission from Ir(ppy)₃.

Example 47

[0396] Composition and Electroluminescent Device ComprisingPoly{2-(5-[4-(octyloxy)phenyl]-1,3,4-oxadiazol-2-yl)phenyl-2,5-diyl}/TPD/Ir(ppy)₃10:3:0.085

[0397] A molecularly doped polymer composition (MDPC) comprising 1000parts toluene (HPLC grade obtained from Aldrich Chemical, Milwaukee,Wis.), 10 parts polymer of Example 16, 3 parts TPD, and 0.085 partsIr(ppy)₃ (all parts by weight) was prepared by combining the componentsand stirring for 1-2 hours at room temperature. The resulting solutionwas filtered through a 0.45 μm polypropylene (PP) syringe filter beforeapplication.

[0398] An OLED lamp was constructed from a portion of this compositionas in Example 32. The lamp construction was:glass/ITO/PEDOT/MDPC/LiF/Al. The lamp exhibited a greenelectroluminescence centered at 513 nm. At a drive current of 20 mA/cm²,the lamp exhibited an external quantum efficiency of 1.99%, a drivevoltage of 7.67 V, and a lamp intensity of 1390 cd/m².

Examples 48-74

[0399] Compositions and Electoluminescent Devices Based on PhenylOxadiazole—9,9-Dioctyl Fluorene Copolymers

[0400] Electroluminescent compositions were prepared as follows: Thepolymers of Example 23 (30% oxadiazole monomer units, Mw=21.3 x 10³) andExample 26 (10% oxadiazole monomer units, Mw=90×10³) were independentlydissolved at 1 weight percent in toluene (HPLC grade obtained fromAldrich Chemical, Milwaukee, Wis.). A hole transporting agent (HTA)selected from TPD, CBP, PVK, HT, TPD-HT, and PS-DPAS was added to somecompositions in a ratio of polymer/HTA =10:0.4, 10:0.8, 10:1.5, 10:3,10:6, or 10:9. The electron transport agent (ETA), PBD, was added tosome compositions in a ratio of polymer/ETA=10:3 or 10:6. Each coatingsolution was filtered through a 0.45 μm polypropylene (PP) syringefilter before application. Specific compositions are shown in Table 4.

[0401] Lamps were constructed as follows: Glass squares of 2 cm×2 cmhaving on one side a vapor deposited coating of indium tin oxide (ITO)were obtained from Thin Film Devices (Anaheim, Calif.). The ITO coatedsides were cleaned with ethanol, treated with an O₂ plasma etch (4 minat 50 W and 200 mTorr), spin coated (2500 rpm for 30 sec) with anaqueous solution of PEDT/PSS, and dried under nitrogen purge at 115° C.Each of the coating solutions prepared above was spin coated on top of aresulting PEDT/PSS coated substrate (2500 rpm for 30 sec). The glasssquares were then mounted into an aluminum frame, introduced into avacuum deposition chamber, and pumped to 10⁻⁶ torr for about 1 hour.Cathodes were applied by vapor depositing about 10 Å of LiF and about2000 Å of aluminum. The resulting organic electroluminescent lamps wereevaluated for drive voltages (V), external percent quantum efficiencies(% Q.E.), luminescence intensities (cd/m²), and emission maxima (δ_(max)nm) for blue, green, and red lamps operating at 20 mA/cm² drive current.

[0402] Tables 4 and 5 summarize these compositions along with theresults of the corresponding lamp performance evaluations. Table 4 showslamp performance data for the LEP of Example 26 (10% oxadiazole monomerunits, Mw=90×10³). Table 5 shows lamp performance data for the LEP ofExample 23 (30% oxadiazole monomer units, Mw=21.3×10³). The polymers,hole transport agents (HTA), and electron transport agents (ETA) arerecorded in Tables 4 and 5 as the number of parts (p) by weight added to1000 parts (1000 p) toluene to make the spin coating solution used inpreparing the lamps. TABLE 4 Electroactive Compositions and OLED DeviceData for Neat and Blended Films Containing the Copolymer of Example 26(Polyfluorene with 10 Mole Percent of Electron Transport OxadiazoleUnits). Electroluminescence data at p Polymer/ p ETA/ p HTA/ 20 mA/cm²1000 p 1000 p 1000 p voltage % Example Toluene Toluene Toluene (V) Q.E.cd/m² λ_(max) nm 48 10 none none 4.56 0.03 2.5 422, 447 49 10 none 3 TPD6.70 0.47 36 424, 448sh 50 10 none 3 HT 6.73 0.84 42 424, 447sh 51 10none 3 TPD and 6.40 0.63 37 420, 447 HT* 52 10 none 3 CBP 5.37 0.06 3.8426, 448 53 10 none 3 PS- 6.47 0.13 7.9 426, 447sh DPAS 54 10 none 3 PVK5.31 0.04 2.6 423, 445sh 55 10 none 6 TPD 5.31 0.14 7.2 424, 448sh 56 10none 9 TPD 4.61 0.03 1.2 424, 448sh 57 10 none 0.4 TPD 7.83 0.29 17 424,448sh 58 10 none 0.8 TPD 8.75 0.35 23 424, 448sh 59 10 none 1.5 TPD 7.340.45 29 424, 448sh 60 10 3 PBD 3 TPD 5.96 0.63 50 424, 450sh 61 10 3 PBD3 HT 5.90 0.71 47 424, 446sh 62 10 6 PBD 3 HT 9.97 0.64 81 425, 445sh

[0403] TABLE 5 Electroactive Compositions and OLED Device Data for Neatand Blended Films Containing the Copolymer of Example 23 (Polyfluorenewith 30 Mole Percent of Electron Transport Oxadiazole Units).Electroluminescence data at p Polymer/ p ETA/ p HTA/ 20 mA/cm² 1000 p1000 p 1000 p voltage % Example Toluene Toluene Toluene (V) Q.E. cd/m²λ_(max) nm 63 10 none none 5.85 0.14  7 423 64 10 none 3 TPD 6.43 0.2923 424 65 10 none 6 TPD 5.31 0.37 39 425, 447sh 66 10 none 9 TPD 5.590.25 35 426, 451sh 67 10 none 1.5 HT 6.65 0.39 32 420, 445sh 68 10 none3 HT 5.44 0.87 54 416, 429sh 69 10 none 6 HT 5.46 0.82 53 425, 447sh 7010 none 9 HT 6.00 0.67 46 427, 448sh 71 10 none 3 CBP 5.98 0.25 16 425,447sh 72 10 none 6 CBP 6.80 0.43 30 424, 447sh 73 10 3 PBD 3 TPD 5.960.71 95 420, 445sh 74 10 3 PBD 3 HT 7.80 1.03 89 420, 445sh

[0404] Tables 4 and 5 show that the neat copolymers of Examples 23 and26 exhibit blue electroluminescence (422 nm, 447 sh) (Examples 48 and63, respectively). At an operating current density of 20 mA/cm², theexternal quantum efficiency for the copolymer of Example 26 was only0.03%, the luminance was only 2.5 cd/m², and the operating voltage was4.6 volts. The copolymer of Example 23 exhibited similar performance.These results are attributed to the absence of a hole transport agent(i.e. lack of charge transport balance).

[0405] Table 4 shows that blending of the copolymer of Example 26 in a10:3 ratio with the hole transport agents TPD, HT, or TPD-HT (Examples49-51) led to improved quantum efficiencies, while emission remainedblue. Green excimer was not observed even after extended operation.Blending of the copolymer of Example 26 with the hole transport agentsCBP, PVK, and PS-DPAS (Examples 52-54) did not result in significantimprovements to the quantum efficiency when compared with the neatpolymers.

[0406] Table 4 also shows that the quantum efficiency droped off quicklyas the TPD content was increased in the amounts LEP/TPD=10:3, 10:6,10:9. Conversely, as the TPD content was decreased below LEP/TPD=10:3the operating voltages began to rise and the efficiencies began to dropoff somewhat. The 10:3 LEP/TPD ratio in the composition with thecopolymer of Example 26 (Example 49) corresponded to approximately a 1:3ratio of oxadiazole functionality to hole transport material.

[0407] Table 4 shows that electron transport properties of the filmswere improved by blending in both hole and electron transport agentswith the copolymer of Example 26. In Examples 60 and 61, blending of thecopolymer of Example 26 with a 1:1 mixture of PBD and either TPD or HTresulted in decreased operating voltages and increases in quantumefficiencies when compared with blends comprising only TPD or HT alone.

[0408] By comparison, when the 9,9-dioctylfluorene homopolymer(Comparative Examples C1 and C2) were blended with a combination of holeand electron transport agents, quantum efficiencies were comparativelyquite poor (for example, 0.059 with 3 parts TPD and 0.037 with 3 partsCBP). The presence of the oxadiazole in the LEP of Example 26 lead to anunexpected improvement in the efficiency of exciton recombination forthe blended systems. This result revealed an important element ofstrategy, useful when attempting to blend commercial LEPs with molecularhole and electron transport materials. The molecular host materials maybe effective at transporting carriers in a blended film, yet beineffective at transferring these carriers into the LEP. Our resultsindicated that for polyfluorenes, incorporation of an electron transportagent as a comonomer into the polymer so as to be conjugated with theLEP enhanced transfer of electrons from the host onto the LEP, resultingin much improved quantum efficiencies for blended systems.

[0409] Table 5 shows the results of an increase in oxadiazole content inthe LEP. Blends of the copolymer of Example 23 (30 mole percentoxadiazole units) with several hole transport agents gave the sametrends observed with the copolymer of Example 26 (10 mole percentoxadiazole units) in Table 4. In all cases, electroluminescence quantumefficiencies improved on going from 10% to 30% oxadiazole comonomerunits. Blends of the copolymer of Example 23 with HT and TPD (Examples64-70 and 73-74) gave the best results; blends with CBP (Examples 71-72)gave lower efficiencies and higher voltages than did blends with HT orTPD, but the contrast was less pronounced than was found for thecopolymer of Example 26.

[0410] Table 5 also shows that the higher oxadiazole content in thecopolymer of Example 23 enabled blending of the polymer with higheramounts of HT, TPD, or CBP without a drop off in quantum efficiency. Forexample, blends with HT in a ratio of LEP/HT=10:3, 10:6, and 10:9(Examples 68-70) gave rise to quantum efficiencies of % QE=0.87, 0.82,and 0.67, respectively. Quantum efficiencies actually improved withincreasing CBP content (Examples 71-72). Finally, blends with both PBDand HT in a 10:3:3 ratio gave even better results (Example 74). Thislamp exhibited clean blue emission with performance numbers as shown (at20 mA/cm²: 6.38 volts 0.97% QE, 105 cd/m²).

[0411] These results show that blended systems useful forelectroluminescent devices and for laser induced thermal imaging of LEPscan be designed using the electroactive polymeric arylenes of thepresent invention as hosts without ruining the quantum efficiency. Thisstrategy can now be achieved by incorporation of the electron transportoxadiazole unit into and in conjugation with the conjugated backbone ofthe polymer to enable charge balance and to shift the relative rates ofintermolecular electron transport governing non-radiative transportthrough the molecular host and radiative transport from the host to theLEP.

Examples 75-83

[0412] Compositions and Electoluminescent Devices Based on PhenylOxadiazole—9,9-Dioctyl Fluorene—Phenylcarbazole Terpolymer

[0413] Electroluminescent compositions and devices were prepared fromthe phenyl oxadiazole—9,9-dioctyl fluorene—phenylcarbazole terpolymer ofExample 25 essentially as described in Examples 48-74. Compositions andlamp evaluation results are summarized in Table 6. In all cases, blueelectroluminescence was observed. TABLE 6 Composition and OLED DeviceData for Neat or Blended Films Prepare with Phenyl Oxadiazole -9,9-Dioctyl Fluorene - Phenylcarbazole Terpolymer p/1000 p p/1000 pp/1000 p Toluene Toluene Toluene Example Polymer ETA HTA λ_(max) nm 7510 none none 419, 445 sh 76 10 none 3 HT 419, 445 sh 77 10 none 6 HT424, 445 sh 78 10 none 3 CBP 421, 445 sh 79 10 none 6 CBP 424, 445 sh 8010 none 3 TPD 420, 445 sh 81 10 none 6 TPD 423, 445 sh 82 10 3 PBD none422, 445 sh 83 10 6 PBD none 425, 445 sh

Example 84

[0414] Preparation of a Donor Sheet

[0415] A thermal transfer donor sheet was prepared in the followingmanner. An LTHC solution, described in Table 7, was coated onto a 0.1 mmthick polyethylene terephthalate (PET) film substrate (M7 from Teijin,Osaka, Japan). Coating was performed using a Yasui Seiki Lab Coater,Model CAG-150, using a microgravure roll with 150 helical cells perinch. The LTHC coating was in-line dried at 80° C. and cured underultraviolet (UV) radiation. TABLE 7 LTHC Solution Parts by ComponentTrade Designation Weight carbon black pigment Raven 760 Ultra ⁽¹⁾ 3.88polyvinyl butyral resin Butvar B-98 ⁽²⁾ 0.69 acrylic resin Joncryl 67⁽³⁾ 2.07 dispersant Disperbyk 161 ⁽⁴⁾ 0.34 fluoro surfactant FC-430 ⁽⁵⁾0.01 epoxy novolac acrylate Ebecryl 629 ⁽⁶⁾ 13.18 acrylic resin Elvacite2669 ⁽⁷⁾ 8.79 2-benzyl-2-(dimethylamino)-1-(4 Irgacure 369 ⁽⁸⁾ 0.89(morpholinyl)phenyl)butanone 1-hydroxycyclohexyl phenyl ketone Irgacure184 ⁽⁸⁾ 0.13 2-butanone 43.75 1,2-propanediol monomethyl ether 26.25acetate

[0416] Next, an interlayer solution, given in Table 8, was coated ontothe cured LTHC layer by a rotogravure coating method using the YasuiSeiki lab coater, Model CAG-150, with a microgravure roll having 180helical cells per lineal inch. This coating was in-line dried at 60° C.and cured under ultraviolet (UV) radiation. TABLE 8 Interlayer CoatingSolution PARTS BY COMPONENT WEIGHT SR 351 HP (trimethylolpropanetriacrylate 14.85 ester, available from Sartomer, Exton, PA) Butvar B-980.93 Joncryl 67 2.78 Irgacure 369 1.25 Irgacure 184 0.19 2-butanone48.00 1-methoxy-2-propanol 32.00

[0417] Next, a transfer layer was formed on the interlayer of the donorsheet. The transfer layer was disposed on the donor sheet by spinningthe molecularly doped polymer composition of Example 47 at about2000-2500 rpm for 30 seconds (Headway Research spincoater) to yield afilm thickness of approximately 50 nm.

Example 85

[0418] Laser Induced Thermal Imaging of Transfer Layer

[0419] Part A

[0420] Preparation of Receptor Substrates

[0421] PEDT (poly(3,4-ethylenedioxythiophene)) solution (Baytron P 4083from Bayer A G, Leverkusen, Germany) diluted 1:1 with deionized water)was filtered through a WHATMAN PURADISC 0.45 μm polypropylene syringefilter.

[0422] Unpatterned ITO(indium tin oxide) glass (Delta Technologies,Stillwater, Minn., less than 100 Ω/square, 1.1 mm thick) wasultrasonically cleaned in a hot, 3% solution of Deconex 12NS detergent(Borer Chemie A G, Zuchwil, Switzerland). The substrates were thenplaced in the Plasma Science plasma treater for surface treatment underthe following conditions: Time:  2 minutes Power: 500 watt (165 W/cm²)Oxygen Flow: 100 Torr

[0423] Immediately after plasma treatment, the PEDT solution wasfiltered and dispensed through a WHATMAN PURADISC 0.45 μm polypropylenesyringe filter onto the ITO substrate. The substrate was then spun(Headway Research spincoater) at 2000 rpm for 30 seconds yielding a PEDTfilm thickness of 40 nm. All of the substrates were heated to 200° C.for 5 minutes under nitrogen.

[0424] Part B

[0425] Laser Induced Thermal Imaging of Transfer Layer from Donor Sheet

[0426] Donor sheets of Example 84 were brought into contact with thereceptor substrates. Next, the donor sheets were imaged using twosingle-mode Nd:YAG lasers. Scanning was performed using a system oflinear galvanometers, with the combined laser beams focused onto theimage plane using an f-theta scan lens as part of a near-telecentricconfiguration. The laser energy density was 0.4 to 0.8 J/cm². The laserspot size, measured at the 1/e² intensity, was 30 micrometers by 350micrometers. The linear laser spot velocity was adjustable between 10and 30 meters per second, measured at the image plane. The laser spotwas dithered perpendicular to the major displacement direction withabout a 100 micrometer amplitude. The transfer layers were transferredas lines onto the receptor substrates, and the intended width of thelines was about 100 micrometers. Laser induced thermal imaging wasperformed at a scan velocity from 11.4 to 20.0 m/s and the conditionsdescribe in Table 9 below. TABLE 9 Laser Induced Thermal ImagingConditions Dose 0.4-0.7 J/cm² Scan speed  20-11.4 m/s Line width  90microns Pitch 225 microns

[0427] Digital images of the resulting laser induced thermal imagingpattern are shown in FIGS. 7 and 8, where the areas, 500, are theunimaged receptor surface, and the areas, 502, are the light emitting,transferred electroactive composition.

[0428] Each of the patents, patent documents, and publications citedabove is hereby incorporated into this document as if reproduced infull.

What is claimed is:
 1. An electroactive polymeric arylene comprising: aconjugated internal region, and end capping groups; wherein theconjugated internal region comprises three or more arylene units, eachof said arylene units being covalently bonded to two adjacent aryleneunits, or to an adjacent arylene unit and to an end capping group;wherein one or more of the arylene units of the internal region have thestructure of Formula I

wherein Ar¹ is a phenylene or naphthylene group arylene that isunsubstituted or substituted with one or more groups selected fromalkyl, alkenyl, alkoxy, fluoro, aryl, fluoroalkyl, heteroalkyl,heteroaryl, and hydrocarbyl containing one or more S, N, O, P, or Siatoms; wherein a is 1 or 2; wherein each E_(y) is independently selectedfrom groups having the structures of Formulas II and III

wherein X is O, S, or NR¹, where R¹ is alkyl, aryl, heteroaryl, orheteroalkyl; wherein each R² is independently alkyl, alkoxy, fluoro,aryl, fluoroalkyl, heteroalkyl, or heteroaryl; wherein b is 0, 1, or 2;wherein Ar² is a carbocyclic aryl group that is unsubstituted orsubstituted with one or more substituents selected from alkyl, alkenyl,alkoxy, fluoro, aryl, fluoroalkyl, heteroalkyl, heteroaryl,alkyloxadiazolyl, aryloxadiazolyl, alkyltriazolyl, aryltriazolyl, andhydrocarbyl containing one or more S, N, O, P, or Si atoms; wherein theend capping groups are each independently selected from carbocyclicaryl, heteroaryl, and tertiary aromatic amino aryl groups that areelectrochemically stable; wherein each end capping group is conjugatedto the conjugated internal region; and wherein each end capping group isunsubstitued or substituted with one or more groups selected from alkyl,alkenyl, alkoxy, aryl, fluoroalkyl, heteroalkyl, heteroaryl, andhydrocarbyl containing one or more S, N, O, P, or Si atoms.
 2. Theelectroactive polymeric arylene of claim 1 further comprising a softsegment; wherein each end capping group is conjugated to the conjugatedinternal region or bonded to the soft segment; and wherein the softsegment is bonded to one or more arylene units of the internal region,or to an end capping group, or to an arylene unit of the internal regionand to an end capping group.
 3. The electroactive polymeric arylene ofclaim 1 wherein each Ar² is independently selected from groups ofFormulas XLIV-LIV

wherein R³ is independently in each case hydrogen, C₁₋₃₀ alkyl, C₁₋₃₀alkenyl, C₆₋₂₀ aryl, C₃₋₂₀ heteroaryl, or C₁₋₃₀ hydrocarbyl containingone or more S, N, O, P, or Si atoms; wherein one or more of the aromaticrings in the groups of Formulas XLIV-LIV are independently unsubstitutedor substituted with one or more groups R^(z); wherein R^(z) isindependently in each case fluoro, C₁₋₂₀ fluoroalkyl, C₁₋₂₀perfluoroalkyl, C₁₋₂₀ alkyl, C₁₋₂₀ alkenyl, C₆₋₂₀ aryl, C₃₋₂₀heteroaryl, C₁₋₃₀ hydrocarbyl containing one or more S, N, O, P, or Siatoms; C₃₋₃₀ alkyloxadiazolyl, C₃₋₃₀ aryloxadiazolyl, C₃₋₃₀alkyltriazolyl, C₃₋₃₀ aryltriazolyl; wherein X is O, S, or NR¹; andwherein R¹ is alkyl, aryl, heteroaryl, or heteroalkyl.
 4. Theelectroactive polymeric arylene of claim 1 wherein the structure ofFormula I is selected from the divalent groups of Formulas XI-XLIII

wherein each of the groups of Formulas XI-XLIII is unsubstituted orsubstituted on one or more of the aromatic rings with one or more groups(R^(y)); wherein R³ is independently in each case hydrogen, C₁₋₃₀ alkyl,C₁₋₃₀ alkenyl, C₆₋₂₀ aryl, C₃₋₂₀ heteroaryl, or C₁₋₃₀ hydrocarbylcontaining one or more S, N, O, P, or Si atoms; and wherein R^(y) isindependently in each case fluoro, C₁₋₂₀ fluoroalkyl, C₁₋₂₀perfluoroalkyl, C₁₋₂₀ alkyl, C₁₋₂₀ alkenyl, C₆₋₂₀ aryl, C₃₋₂₀heteroaryl, or C₁₋₃₀ hydrocarbyl containing one or more S, N, O, P, orSi atoms.
 5. The electroactive polymeric arylene of claim 1 wherein theelectroactive polymeric arylene is a polymer of the Formula V

wherein each EC is an end capping group independently selected fromcarbocyclic aryl, heteroaryl, and tertiary aromatic amino aryl groupsthat are electrochemically stable, and n is an integer in the range of 3to 100,000.
 6. The electroactive polymeric arylene of claim 5 whereinone or both of Ar² and EC is substituted with one or more groupsselected from fluoro, fluoroalkyl, and perfluoroalkyl, with the provisothat when EC is phenyl the fluoro group is not in the para position. 7.The electroactive polymeric arylene of claim 1 wherein the carbocyclicaryl end capping groups are each independently selected from phenyl,naphthyl, acenaphthyl, phenanthryl, anthracenyl, fluorenyl,9-silafluorenyl, dihydrophenathrenyl, tetrahydropyrenyl, perylenyl,spirobisfluorenyl, fluoranthenyl, pyrenyl, rubrenyl, chrysenyl,biphenyl, and benzo[g,h,i]perylenyl; wherein the heteroaryl end cappinggroups are each independently selected from furyl, thiophenyl, pyrrolyl,imidazolyl, pyrazolyl, triazolyl, tetrazolyl, thiazolyl, oxazolyl,isoxazolyl, oxadiazolyl, thiadiazolyl, isothiazolyl, pyridinyl,pyridazinyl, pyrazinyl, pyrimidinyl, quinolinyl, isoquinolinyl,benzofuryl, benzothiophenyl, indolyl, carbazoyl, benzoxazolyl,benzothiazolyl, benzimidazolyl, cinnolinyl, quinazolinyl, quinoxalinyl,phthalazinyl, benzothiadiazolyl, benzotriazinyl, phenazinyl,phenanthridinyl, acridinyl, indazolyl, and siloles; wherein the tertiaryaromatic amino aryl end capping groups are each independently selectedfrom monovalent aromatic ring radicals of tertiary aromatic aminesselected from diarylanilines, alkylcarbazole, arylcarbazole,tetraarylediamines, N,N,N′N′-tetraarylbenzidines,N,N,N′,N′-tetraaryl-1,4-phenylenediamines, N,N,N′N′-tetraryl-2,7-diaminofluorenes,N,N′-bis(3-methylphenyl)-N,N′-bis(phenyl)benzidine,N,N′-bis(3-naphthalen-2-yl)-N,N′-bis(phenyl)benzidine,1,4-bis(carbazolyl)biphenyl, peraryltriamines, starburst amines,4,4′,4″-tris(N,N-diarylamino)triphenylamines,1,3,5-tris(4-diarylaminophenyl)benzenes,4,4′,4″-tris(N,N-diphenylamino)triphenylamine,4,4′,4″-tris(N-3-methylphenyl-N-phenylamino)triphenylamine;1,3,5-Tris(4-diphenylaminophenyl)benzenes, dendridic amines, and spiroamines; and wherein the end capping groups are unsubstituted orsubstituted with one or more groups selected from the group consistingof C₁₋₂₀ fluoroalkyl, C₁₋₂₀ perfluoroalkyl, C₁₋₂₀ alkyl, C₁₋₂₀ alkenyl,C₆₋₂₀ aryl, C₃₋₂₀ heteroaryl, C₁₋₃₀ hydrocarbyl containing one or moreS, N, O, P, or Si atoms, C₃₋₃₀ alkyloxadiazolyl, C₃₋₃₀ aryloxadiazolyl,C₃₋₃₀ alkyltriazolyl, and C₃₋₃₀ aryltriazolyl.
 8. The electroactivepolymeric arylene of claim 1 wherein the structure of Formula I isselected from the divalent groups of Formulas XI-XLIII

wherein each of the groups of Formulas XI-XLIII is unsubstituted orsubstituted on one or more of the aromatic rings with one or more groups(R^(y)); wherein R^(y) is independently in each case fluoro, C₁₋₂₀fluoroalkyl, C¹⁻²⁰ perfluoroalkyl, C₁₋₂₀ alkyl, C₁₋₂₀ alkenyl, C₆₋₂₀aryl, C₃₋₂₀ heteroaryl, or C₁₋₃₀ hydrocarbyl containing one or more S,N, O, P, or Si atoms; wherein R³ is independently in each case hydrogen,C₁₋₃₀ alkyl, C₁₋₃₀ alkenyl, C₆₋₂₀ aryl, C₃₋₂₀ heteroaryl, or C₁₋₃₀hydrocarbyl containing one or more S, N, O, P, or Si atoms; wherein eachAr² is independently selected from groups of Formulas XLIV-LIV

wherein one or more of the aromatic rings in the groups of FormulasXLIV-LIV are independently unsubstituted or substituted with one or moregroups R^(z); wherein R^(z) is independently in each case fluoro, C₁₋₂₀fluoroalkyl, C₁₋₂₀ perfluoroalkyl, C₁₋₂₀ alkyl, C₁₋₂₀ alkenyl, C₆₋₂₀aryl, C₃₋₂₀ heteroaryl, C₁₋₃₀ hydrocarbyl containing one or more S, N,O, P, or Si atoms; C₃₋₃₀ alkyloxadiazolyl, C₃₋₃₀ aryloxadiazolyl, C₃₋₃₀alkyltriazolyl, C₃₋₃₀ aryltriazolyl; wherein X is O, S, or NR¹; whereinR¹ is alkyl, aryl, heteroaryl, or heteroalkyl; wherein R³ isindependently in each case hydrogen, C₁₋₃₀ alkyl, C₁₋₃₀ alkenyl, C₆₋₂₀aryl, C₃₋₂₀ heteroaryl, or C₁₋₃₀ hydrocarbyl containing one or more S,N, O, P, or Si atoms; wherein the carbocyclic aryl end capping groupsare each independently selected from phenyl, naphthyl, acenaphthyl,phenanthryl, anthracenyl, fluorenyl, 9-silafluorenyl,dihydrophenathrenyl, tetrahydropyrenyl, perylenyl, spirobisfluorenyl,fluoranthenyl, pyrenyl, rubrenyl, chrysenyl, biphenyl, andbenzo[g,h,i]perylenyl; wherein the heteroaryl end capping groups areeach independently selected from furyl, thiophenyl, pyrrolyl,imidazolyl, pyrazolyl, triazolyl, tetrazolyl, thiazolyl, oxazolyl,isoxazolyl, oxadiazolyl, thiadiazolyl, isothiazolyl, pyridinyl,pyridazinyl, pyrazinyl, pyrimidinyl, quinolinyl, isoquinolinyl,benzofuryl, benzothiophenyl, indolyl, carbazoyl, benzoxazolyl,benzothiazolyl, benzimidazolyl, cinnolinyl, quinazolinyl, quinoxalinyl,phthalazinyl, benzothiadiazolyl, benzotriazinyl, phenazinyl,phenanthridinyl, acridinyl, indazolyl, and siloles; wherein the tertiaryaromatic amino aryl end capping groups are each independently selectedfrom monovalent aromatic ring radicals of tertiary aromatic aminesselected from diarylanilines, alkylcarbazole, arylcarbazole,tetraarylediamines, N,N,N′N′-tetraarylbenzidines,N,N,N′,N′-tetraaryl-1,4-phenylenediamines, N,N,N′N′-tetraryl-2,7-diaminofluorenes,N,N′-bis(3-methylphenyl)-N,N′-bis(phenyl)benzidine,N,N′-bis(3-naphthalen-2-yl)-N,N′-bis(phenyl)benzidine,1,4-bis(carbazolyl)biphenyl, peraryltriamines, starburst amines,4,4′,4″-tris(N,N-diarylamino)triphenylamines,1,3,5-tris(4-diarylaminophenyl)benzenes,4,4′,4″-tris(N,N-diphenylamino)triphenylamine,4,4′,4″-tris(N-3-methylphenyl-N-phenylamino)triphenylamine;1,3,5-Tris(4-diphenylaminophenyl)benzenes, dendridic amines, and spiroamines; and wherein the end capping groups are unsubstituted orsubstituted with one or more groups selected from the group consistingof C₁₋₂₀ fluoroalkyl, C₁₋₂₀ perfluoroalkyl, C₁₋₂₀ alkyl, C₁₋₂₀ alkenyl,C₆₋₂₀ aryl, C₃₋₂₀ heteroaryl, C₁₋₃₀ hydrocarbyl containing one or moreS, N, O, P, or Si atoms, C₃₋₃₀ alkyloxadiazolyl, C₃₋₃₀ aryloxadiazolyl,C₃₋₃₀ alkyltriazolyl, and C₃₋₃₀ aryltriazolyl.
 9. The electroactivepolymeric arylene of claim 1 wherein the end capping groups are eachindependently selected from the group of Formulas LXVIII-LXXXVII

wherein R³ is independently in each case hydrogen, C₁₋₃₀ alkyl, C₁₋₃₀alkenyl, C₆₋₂₀ aryl, C₃₋₂₀ heteroaryl, or C₁₋₃₀ hydrocarbyl containingone or more S, N, O, P, or Si atoms, and wherein any of the aromatic oraliphatic rings can be independently substituted one or more times withfluoro, C₁₋₂₀ fluoroalkyl, C₁₋₂₀ perfluoroalkyl, C₁₋₂₀ alkyl, C₁₋₂₀alkenyl, C₆₋₂₀ aryl, C₃₋₂₀ heteroaryl, or C₁₋₃₀ hydrocarbyl containingone or more S, N, O, P, or Si atoms.
 10. The electroactive polymericarylene of claim 1 wherein the electroactive polymeric arylene is acopolymer; wherein one or more of the arylene units are comonomer unitsindependently selected from carbocyclic arylene, heteroarylene, andtertiary aromatic amino arylene; wherein the comonomer units areconjugated with Ar¹; and wherein the comonomer units are unsubstitutedor substituted with one or more groups independently selected fromalkyl, alkenyl, alkoxy, fluoro, aryl, fluoroalkyl, heteroalkyl,heteroaryl, and hydrocarbyl containing one or more S, N, O, P, or Siatoms.
 11. The electroactive polymeric arylene of claim 10 wherein theelectroactive polymeric arylene is a copolymer of Formula VI, VII, orVIII

wherein Ar³ and Ar⁴ are comonomer units, each independently selectedfrom C₆₋₂₀ carbocyclic arylenes, C₃₋₂₀ heteroarylenes, and C₁₈₋₆₀tertiary aromatic amino arylenes; where Ar³ and Ar⁴ are unsubstituted orsubstituted with one or more substituents selected from alkyl, fluoro,fluoroalkyl, aryl, heteroaryl, and hydrocarbyl containing one or more S,N, O, P, or Si atoms; wherein m and n are integers in the range of 2 to100,000; wherein EC are end capping groups which are the same ordifferent and which are electrochemically stable carbocyclic aryl,heteroaryl, or tertiary aromatic amino aryl groups; and wherein thecopolymer is a random, alternating, or block copolymer.
 12. Theelectroactive polymeric arylene of claim 11 wherein the copolymercomprises a soft segment.
 13. The electroactive polymeric arylene ofclaim 11 wherein one or more of Ar², EC, Ar³, and Ar⁴ are substitutedwith one or more groups independently selected from fluoro, fluoroalkyl,and perfluoroalkyl with the proviso that when EC is phenyl the fluorogroup is not in the para position.
 14. The electroactive polymericarylene of claim 11 wherein one or both of Ar³ and Ar⁴ are fluorenyleneof Formula LXXXIX

wherein R³ is independently in each case selected from hydrogen, C₁₋₃₀alkyl, C₁₋₃₀ alkenyl, C₆₋₂₀ aryl, C₃₋₂₀ heteroaryl, and C₁₋₃₀hydrocarbyl containing one or more S, N, O, P, or Si atoms; whereinR^(y) is independently in each case selected from fluoro, C₁₋₂₀fluoroalkyl, C¹⁻²⁰ perfluoroalkyl, C₁₋₂₀ alkyl, C₁₋₂₀ alkenyl, C₆₋₂₀aryl, C₃₋₂₀ heteroaryl, and C₁₋₃₀ hydrocarbyl containing one or more S,N, O, P, or Si atoms; and wherein n is 0, 1, or
 2. 15. The electroactivepolymeric arylene of claim 11 wherein the electroactive polymericarylene is an alternating or block copolymer.
 16. The electroactivepolymeric arylene of claim 11 wherein Ar³ and Ar⁴ are independentlyselected from phenylene group arylene and naphthalene group arylene;wherein each phenylene group arylene and naphthalene group arylene isindependently unsubstituted or substituted with one or more substituentsselected independently in each case from fluoro, C₁₋₂₀ fluoroalkyl,C₁₋₂₀ perfluoroalkyl, C₁₋₂₀ alkyl, C₆₋₂₀ aryl, C₃₋₂₀ heteroaryl, andC₁₋₃₀ hydrocarbyl containing one or more S, N, O, P, or Si atoms. 17.The electroactive polymeric arylene of claim 11 wherein Ar³ and Ar⁴ areindependently selected from condensed polycyclic arylene, heteroarylene,and tertiary aromatic amino arylene; wherein each condensed polycyclicarylene, heteroarylene, and tertiary aromatic amino arylene isindependently unsubstituted or substituted with one or more substituentsselected independently in each case from C₁₋₂₀ alkyl, C₆₋₂₀ aryl, C₃₋₂₀heteroaryl, and C₁₋₃₀ hydrocarbyl containing one or more S, N, O, P, orSi atoms.
 18. The electroactive polymeric arylene of claim 1 wherein theelectroactive polymeric arylene remains amorphous at temperatures aboveits glass transition temperature.
 19. The electroactive polymericarylene of claim 1 wherein the electroactive polymeric arylene is lightemitting; and wherein the color of the light emission is stable duringthermal aging.
 20. The electroactive polymeric arylene of claim 19wherein the color is blue.
 21. A monomer having the structure of FormulaIV

wherein each D is a reactive group independently selected from chlorine,bromine, iodine, boronic acid, and boronic ester; wherein—Ar¹(E_(y))_(a)- is selected from Formulas CLXV and CLXVI

wherein R^(y) is independently in each case fluoro, C₁₋₂₀ fluoroalkyl,C₁₋₂₀ perfluoroalkyl, C₁₋₂₀ alkyl, C₁₋₂₀ alkenyl, C₆₋₂₀ aryl, C₃₋₂₀heteroaryl, or C₁₋₃₀ hydrocarbyl containing one or more S, N, O, P, orSi atoms; n is 0, 1,or 2; a is 1 or 2; E_(y) is Formula II

where X is selected from —S—, and —N(R¹)—, or Ey is Formula III

where X is selected from —O—, —S—, and —N(R¹)— wherein R¹ is alkyl,aryl, heteroaryl, or heteroalkyl; wherein each R² is independentlyalkyl, alkenyl, alkoxy, fluoro, aryl, fluoroalkyl, heteroalkyl, orheteroaryl; wherein b is 0, 1, or 2; wherein Ar² is a carbocyclic arylgroup selected from phenyl, biphenyl, naphthyl, anthracenyl, fluorenyl,9-silafluorenyl, spirobisfluorenyl, dihydrophenanthrolinyl,dihydropyrenyl, tetrahydropyrenyl, pyrenyl, and perylenyl; and whereinAr² is unsubstituted or substituted on one or more of the aromatic ringswith one or more groups selected from alkyl, alkenyl, alkoxy, fluoro,aryl, fluoroalkyl, heteroalkyl, heteroaryl, alkyloxadiazolyl,aryloxadiazolyl, alkyltriazolyl, aryltriazolyl, and hydrocarbylcontaining on or more S, N, O, P, or Si atoms.
 22. A monomer of claim 21wherein —Ar¹(E_(y))_(a)- is selected from Formulas CXI-CXIII andCXIV-CXVI

wherein X is selected from —O—, —S—, and —N(R¹)—, and

wherein X is selected from —S—, and —N(R¹)—.
 23. A monomer of claim 22selected from the group consisting of Compounds 1, 2, and 4-14


24. A monomer having the structure of Formula IV

wherein each D is a reactive group independently selected from chlorine,bromine, iodine, boronic acid, and boronic ester; wherein—Ar¹(E_(y))_(a)- is selected from Formulas XIV-XLIII

wherein each of the Formulas XIV-XLIII is independently unsubstituted orsubstituted on one or more of the aromatic rings with one or more R^(y):wherein each R^(y) is independently selected from fluoro, C₁₋₂₀fluoroalkyl, C₁₋₂₀ perfluoroalkyl, C₁₋₂₀ alkyl, C₁₋₂₀ alkenyl, C₆₋₂₀carbocyclic aryl, C₃₋₂₀ heteroaryl, and C₁₋₃₀ hydrocarbyl containing oneor more S, N, O, P, or Si atoms; wherein each R³ is independentlyselected from hydrogen, C₁₋₃₀ alkyl, C₁₋₃₀ alkenyl, C₆₋₂₀ carbocyclicaryl, C₃₋₂₀ heteroaryl, or C₁₋₃₀ hydrocarbyl containing one or more S,N, O, P, or Si atoms; wherein 1 or 2 E_(y) groups are present; whereineach E_(y) is independently selected from groups having the structuresof Formulas II and III

wherein X is O, S, or NR¹, where R¹ is alkyl, aryl, heteroaryl, orheteroalkyl; wherein each R² is independently selected from alkyl,alkenyl, alkoxy, fluoro, aryl, fluoroalkyl, heteroalkyl, and heteroaryl;wherein b is 0, 1, or 2; wherein Ar² is a carbocyclic aryl groupselected from phenyl, biphenyl, naphthyl, anthracenyl, fluorenyl,9-silafluorenyl, spirobisfluorenyl, dihydrophenanthrolinyl,dihydropyrenyl, tetrahydropyrenyl, pyrenyl, and perylenyl; and whereinAr² is unsubstituted or substituted on one or more of the aromatic ringswith one or more groups selected from alkyl, alkenyl, alkoxy, fluoro,aryl, fluoroalkyl, heteroalkyl, heteroaryl, alkyloxadiazolyl,aryloxadiazolyl, alkyltriazolyl, aryltriazolyl, and hydrocarbylcontaining one or more S, N, O, P, or Si atoms.
 25. A monomer of claim24 wherein the monomer is selected from Formulas CXVII, CXVIII, and CXIX

wherein Q is phenylene or a bond; R^(z) is present or not present; andeach R^(z) is independently selected from fluoro, C₁₋₂₀ fluoroalkyl,C₁₋₂₀ perfluoroalkyl, C₁₋₂₀ alkyl, C₁₋₂₀ alkenyl, C₆₋₂₀ aryl, C₃₋₂₀heteroaryl, C₁₋₃₀ hydrocarbyl containing one or more S, N, O, P, or Siatoms; C₃₋₃₀ alkyloxadiazolyl, C₃₋₃₀ aryloxadiazolyl, C₃₋₃₀alkyltriazolyl, and C₃₋₃₀ aryltriazolyl.
 26. A monomer of claim 24wherein the monomer is Compound 15


27. An electroactive composition comprising the electroactive polymericarylene of claim
 1. 28. The electroactive composition of claim 27further comprising one or more materials selected from hole transportmaterial, electron transport material, binder, polymeric binder,molecule emitters, light emitting polymers, waveguiding particles,phosphorescent compounds, color conversion material, and one or moredifferent electroactive polymeric arylene homopolymers, copolymers, orcombinations thereof; wherein the electroactive composition iselectroluminescent.
 29. The electroactive composition of claim 28wherein the composition is solution processible.
 30. The electroactivecomposition of claim 28 comprising a light emitting polymer or amolecular emitter; wherein the electroactive composition supports bothhole transport and electron transport; and wherein the composition issolution processible.
 31. The electroactive composition of claim 28comprising one or more materials selected from hole transport polymers,hole transport monomers, electron transport monomers, and inertpolymeric binders; wherein the electroactive polymeric arylene is acopolymer; and wherein the electroactive composition supports both holetransport and electron transport.
 32. An organic electronic devicecomprising the electroactive polymeric arylene of claim
 1. 33. Theorganic electronic device of claim 32 wherein the organic electronicdevice is an organic electroluminescent device.
 34. The organicelectroluminescent device of claim 33 comprising a device layer, asubstrate, and optionally an optical element; wherein the device layercomprises the electroactive polymeric arylene.
 35. The organicelectroluminescent device of claim 34 wherein the device layer includesone or more organic electroluminescent elements.
 36. The organicelectroluminescent device of claim 35 wherein a plurality of organicelectroluminescent elements are adjacent to each other; and wherein twoor more adjacent elements emit different colors of light.
 37. Theorganic electroluminescent device of claim 35 wherein one or more of theorganic electroluminescent elements is an organic light emitting diodeincluding an anode, a cathode, a light emitting layer, and one or bothof a hole transport layer and an electron transport layer; and whereinone or both of the light emitting layer and the electron transport layerif present includes the electroactive polymeric arylene.
 38. A donorsheet, comprising a substrate, a light-to-heat conversion layer, and atransfer layer comprising the electroactive composition of claim 27.